Solubilized defoamers for cementitious compositions

ABSTRACT

Amine solubilizing agents are mixed with water insoluble defoamers and optionally a dispersant for cementitious compositions to provide an admixture for cementitious compositions that is stable over time. A cementitious composition is provided that includes cementitious material, water, a water insoluble defoamer, optionally a dispersant for cementitious compositions, and an amine solubilizing agent that solubilizes the water insoluble defoamer. A method is provided for making a cementitious composition that includes mixing cementitious material, water, a water insoluble defoamer, an amine solubilizing agent that solubilizes the water insoluble defoamer, and optionally a dispersant for cementitious compositions.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a continuation in part of U.S. Ser. No. 09/732,380,filed on Dec. 7, 2000 now U.S. Pat. No. 6,569,924 which claims priorityfrom U.S. Provisional Patent Application No. 60/170,062, filed Dec. 10,1999, both of which are incorporated herein by reference.

BACKGROUND

Hydraulic cements, such as Portland cement, are used to form structuralformations. Hydraulic cements can be mixed with aggregate to formmortars, which additionally include small aggregate and water, orconcrete, which are mortars which additionally include large aggregate.

When working with hydraulic cements, it is desired to increase the slumpproperties of the initially formed hydraulic cement composition to aidin placement of the composition and to extend the period of flowabilityin order to provide adequate time to complete placement of thecementitious composition. Admixtures can be added to hydraulic cement toincrease the slump. Additionally, admixtures can be added that alsoreduce the amount of water required and to produce flowable cementitiouscompositions. The reduced water content increases the strength andimproves the durability of the resulting hydraulic cement formation.

One admixture for increasing the flowability and reducing the watercontent is a polycarboxylate dispersant. Polycarboxylate dispersants arepolymers with a carbon backbone with pendant side chains, wherein atleast a portion of the side chains are attached to the backbone througha carboxyl group or an ether group. Polycarboxylate dispersants are veryeffective at dispersing and reducing the water content in hydrauliccements.

One drawback to polycarboxylate dispersants is that they have a tendencyto entrain air in the cementitious composition during mixing. While someentrained air may be desired for particular applications, such asproviding freeze-thaw durability to the cementitious composition, anexcess of entrained air is detrimental to the compressive strength ofthe resulting hydraulic formation.

Generally in the construction industry, non-air entrained cementitiouscompositions having an air content of less than 3% is desired, with anair content of less than 2% being preferred. Air entraining admixturesare sometimes used to provide purposeful air contents of 5-8% whichimproves the freeze thaw durability of the cementitious mixture. Whenthis is the case, it is desirable to be able to adjust the air contentby changing the air entrainer dosage and to have the resulting airremain stable over time.

To overcome the excess entraining of air in cementitious compositions,defoamers have been added to the cementitious mix to reduce the aircontent to a desired level. Defoamers typically have been included withthe polycarboxylate admixture. However, the defoamers used in the priorart have been non-water-soluble compositions used alone. The problemwith non-water-soluble defoamers is that they give an inadequatelong-term storage stability to the admixture resulting, in phaseseparation. The polycarboxylate dispersant is generally a water solubledispersant. When a non-water-soluble defoamer is used in conjunctionwith a water-soluble dispersant, the mixture separates over time. Thisrequires that the mixture be mixed prior to use. Also, some insolubledefoamers can cause unpredictable air contents over time.

Another technique used in the prior art has been the grafting of thedefoamer onto the dispersant molecule.

The prior art, however, has not shown the combination of a defoamer thatis not chemically combined with the polycarboxylate dispersant that isused in conjunction with an amine solubilizing or stabilizing agent.

What is needed in the industry is a combination of a water insolubledefoamer, a dispersant for cementitious compositions, and an aminesolubilizing agent that solubilizes or stabilizes the water insolubledefoamer that produces controllable air contents in non-air entrainedand air entrained cementitious compositions.

SUMMARY

Amine solubilizing agents can be combined with water insoluble defoamersand dispersants for cementitious compositions to provide an admixturefor cementitious compositions that is stable over time. The resultingadmixture has long term storage stability so that the admixture does notneed to be mixed prior to use at the work site.

An admixture composition for cementitious compositions is provided thatcomprises a water insoluble defoamer, an amine solubilizing agent thatsolubilizes the water insoluble defoamer, and optionally a dispersantfor cementitious compositions.

A cementitious composition is provided that comprises cementitiousmaterial, water, a water insoluble defoamer, an amine solubilizing agentthat solubilizes the water insoluble defoamer, and optionally adispersant for cementitious compositions.

A method of making a cementitious composition is provided that comprisesmixing cementitious material, water, a water insoluble defoamer, anamine solubilizing agent that solubilizes the water insoluble defoamer,and optionally a dispersant for cementitious compositions.

DETAILED DESCRIPTION

A combination of amine solubilizing agents that is effective as asolubilizing agent in the salt form and deactivated at an alkaline pHand defoamers are provided that are used in conjunction with adispersant for cementitious compositions to control air contents incementitious compositions.

The term amine solubilizing agent refers to a material that cansolubilize insoluble material. Solubilization is defined as a mode ofbringing into solution substances that are otherwise insoluble in agiven medium. Solubilization involves the previous presence of acolloidal (organized) solution whose particles take up and incorporatewithin or upon themselves the otherwise insoluble material. (M. E. L.McBain and E. Hutchinson, Solubilization and Related Phenomena, AcademicPress, New York (1955). Generally, an amine solubilizing agent is asolubilizing surfactant. The amine solubilizing agents that are presentin the invention may include but are not limited to amine solubilizingagents sold by Akzo Nobel Surface Chemistry, LLC (Chicago, Ill.),Corsicana Technologies, Inc. (Dallas, Tex.), Croda, Inc. (New York,N.Y.), Scher Chemicals, Inc., Lonza, Inc. (Switzerland), ColonialChemical Company (South Pittsburg, Tenn.), Tomah Products, Inc.(Milton,Wis.), Uniqema (USA Contact—New Castle, Del.), and Stepan Company(Northfield, Ill.).

The term dispersant for cementitious compositions throughout thisspecification includes polycarboxylate dispersants and oligomericdispersants.

The term polycarboxylate dispersant throughout this specification refersto polymers with a carbon or polyamide backbone with pendant sidechains, wherein at least a portion of the side chains are attached tothe backbone through a carboxyl group or an ether group. The termdispersant is also meant to include those chemicals which also functionas a plasticizer, water reducer, fluidizer, antiflocculating agent, orsuperplasticizer for cementitious compositions. Examples ofpolycarboxylate dispersants can be found in U.S. Ser. No. 09/937,810,U.S. Pat. No. 6,267,814, U.S. Pat. No. 6,290,770, U.S. Pat. No.6,310,143, U.S. Pat. No. 6,211,317, U.S. Pat. No. 6,187,841, U.S. Pat.No. 5,158,996, U.S. Pat. No. 6,008,275, U.S. Pat. No. 6,136,950, U.S.Pat. No. 6,284,867, U.S. Pat. No. 5,609,681, U.S. Pat. No. 5,494,516;U.S. Pat. No. 5,674,929, U.S. Pat. No. 5,660,626, U.S. Pat. No.5,668,195, U.S. Pat. No. 5,661,206, U.S. Pat. No. 5,358,566, U.S. Pat.No. 5,162,402, U.S. Pat. No. 5,798,425, U.S. Pat. No. 5,612,396, U.S.Pat. No. 6,063,184, and U.S. Pat. No. 5,912,284, U.S. Pat. No.5,840,114, U.S. Pat. No. 5,753,744, U.S. Pat. No. 5,728,207, U.S. Pat.No. 5,725,657, U.S. Pat. No. 5,703,174, U.S. Pat. No. 5,665,158, U.S.Pat. No. 5,643,978, U.S. Pat. No. 5,633,298, U.S. Pat. No. 5,583,183,and U.S. Pat. No. 5,393,343, which are incorporated herein by reference.

The term oligomenic dispersant throughout this specification refers tooligomers that are a reaction product of a component A, optionallycomponent B, and component C that are defined in U.S. Pat. No.6,133,347, U.S. Pat. No. 6,451,881, and U.S. Pat. No. 6,492,461, whichre hereby incorporated by reference.

The dispersants used in combination with the water insoluble defoamerand the amine solubilizing agent that solubilizes the water insolubledefoamer are at least one of:

-   -   a) a dispersant of Formula (I):        -   wherein in Formula (I)        -   X is at least one of hydrogen, an alkali earth metal ion, an            alkaline earth metal ion, ammonium ion, or amine;        -   R is at least one of C₁ to C₆ alkyl(ene) ether or mixtures            thereof or C₁ to C₆ alkyl(ene) imine or mixtures thereof;        -   Q is at least one of oxygen, NH, or sulfur;        -   p is a number from 1 to about 300 resulting in at least one            of a linear side chain or branched side chain;        -   R₁ is at least one of hydrogen, C₁ to C₂₀ hydrocarbon, or            functionalized hydrocarbon containing at least one of —OH,            —COOH, an ester or amide derivative of —COOH, sulfonic acid,            an ester or amide derivative of sulfonic acid, amine, or            epoxy;        -   Y is at least one of hydrogen, an alkali earth metal ion, an            alkaline earth metal ion, ammonium ion, amine, a hydrophobic            hydrocarbon or polyalkylene oxide moiety that functions as a            defoamer;        -   m, m′, m″, n, n′, and n″ are each independently 0 or an            integer between 1 and about 20;        -   Z is a moiety containing at least one of i) at least one            amine and one acid group, ii) two functional groups capable            of incorporating into the backbone selected from the group            consisting of dianhydrides, dialdehydes, and            di-acid-chlorides, or iii) an imide residue; and        -   wherein a, b, c, and d reflect the mole fraction of each            unit wherein the sum of a, b, c, and d equal one, wherein a,            b, c, and d are each a value greater than or equal to zero            and less than one, and at least two of a, b, c, and d are            greater than zero;    -   b) a dispersant of Formula (II):        -   wherein in Formula (II):        -   A is COOM or optionally in the “y” structure an acid            anhydride group (—CO—O—CO—) is formed in place of the A            groups between the carbon atoms to which the A groups are            bonded to form an anhydride;        -   B is COOM        -   M is hydrogen, a transition metal cation, the residue of a            hydrophobic polyalkylene glycol or polysiloxane, an alkali            metal ion, an alkaline earth metal ion, ferrous ion,            aluminum ion, (alkanol)ammonium ion, or (alkyl)ammonium ion;        -   R is a C₂₋₆ alkylene radical;        -   R₁ is a C₁₋₂₀ alkyl, C₆₋₉ cycloalkyl, or phenyl group;        -   x, y, and z are a number from 0.01 to 100;        -   m is a number from 1 to 100; and        -   n is a number from 10 to 100;    -   c) a dispersant comprising at least one polymer or a salt        thereof having the form of a copolymer of        -   i) a maleic anhydride half-ester with a compound of the            formula RO(AO)_(m)H, wherein R is a C₁-C₂₀ alkyl group, A is            a C₂₋₄ alkylene group, and m is an integer from 2-16; and        -   ii) a monomer having the formula CH₂═CHCH₂—(OA)_(n)OR,            wherein n is an integer from 1-90 and R is a C₁₋₂₀ alkyl            group;    -   d) a dispersant obtained by copolymerizing 5 to 98% by weight of        an (alkoxy)polyalkylene glycol mono(meth)acrylic ester        monomer (a) represented by the following general formula (1):        -   wherein R₁ stands for hydrogen atom or a methyl group, R₂O            for one species or a mixture of two or more species of            oxyalkylene group of 2 to 4 carbon atoms, providing two or            more species of the mixture may be added either in the form            of a block or in a random form, R₃ for a hydrogen atom or an            alkyl group of 1 to 5 carbon atoms, and m is a value            indicating the average addition mol number of oxyalkylene            groups that is an integer in the range of 1 to 100, 95 to 2%            by weight of a (meth)acrylic acid monomer (b) represented by            the above general formula (2), wherein R₄ and R₅ are each            independently a hydrogen atom or a methyl group, and M₁ for            a hydrogen atom, a monovalent metal atom, a divalent metal            atom, an ammonium group, or an organic amine group, and 0 to            50% by weight of other monomer (c) copolymerizable with            these monomers, provided that the total amount of (a), (b),            and (c) is 100% by weight;    -   e) a graft polymer that is a polycarboxylic acid or a salt        thereof, having side chains derived from at least one species        selected from the group consisting of oligoalkyleneglycols,        polyalcohols, polyoxyalkylene amines, and polyalkylene glycols;    -   f) a reaction product of component A, optionally component B,        and component C;        -   wherein each component A is independently a nonpolymeric,            multi-functional moiety or combination of mono or            multifunctional moieties that adsorbs onto a cementitious            particle, and contains at least one residue derived from a            first component selected from the group consisting of            phosphates, phosphonates, phosphinates, hypophosphites,            sulfates, sulfonates, sulfinates, alkyl trialkoxy silanes,            alkyl triacyloxy silanes, alkyl triaryloxy silanes, borates,            boronates, boroxines, phosphoramides, amines, amides,            quaternary ammonium groups, carboxylic acids, carboxylic            acid esters, alcohols, carbohydrates, phosphate esters of            sugars, borate esters of sugars, sulfate esters of sugars,            salts of any of the preceding moieties, and mixtures            thereof;        -   wherein component B is an optional moiety, where if present,            each component B is independently a nonpolymeric moiety that            is disposed between the component A moiety and the component            C moiety, and is derived from a second component selected            from the group consisting of linear saturated hydrocarbons,            linear unsaturated hydrocarbons, saturated branched            hydrocarbons, unsaturated branched hydrocarbons, alicyclic            hydrocarbons, heterocyclic hydrocarbons, aryl, phosphoester,            nitrogen containing compounds, and mixtures thereof; and        -   wherein component C is at least one moiety that is a linear            or branched water soluble, nonionic polymer substantially            non-adsorbing to cement particles, and is selected from the            group consisting of poly(oxyalkylene glycol),            poly(oxyalkylene amine), poly(oxyalkylene diamine),            monoalkoxy poly(oxyalkylene amine), monoaryloxy            poly(oxyalkylene amine), monoalkoxy poly(oxyalkylene            glycol), monoaryloxy poly(oxyalkylene glycol), poly(vinyl            pyrrolidones), poly(methyl vinyl ethers), poly(ethylene            imines), poly(acrylamides), polyoxazoles, and mixtures            thereof; and    -   g) a dispersant of Formula (III):        -   wherein in Formula (III):        -   D=a component selected from the group consisting of the            structure d1, the structure d2, and mixtures thereof;        -   X=H, CH₃, C₂ to C₆ Alkyl, Phenyl, p-Methyl Phenyl, or            Sulfonated Phenyl;        -   Y=H or —COOM;        -   R=H or CH₃;        -   Z=H, —SO₃M, —PO₃M, —COOM, —O(CH₂)_(n)OR₃ where n=2 to 6,            —COOR₃, or —(CH₂)_(n)OR₃ where n=0 to 6, —CONHR₃,            —CONHC(CH₃)₂ CH₂SO₃M, —COO(CHR₄)_(n)OH where n=2 to 6, or            —O(CH₂)_(n)OR₄ wherein n=2 to 6;        -   R₁, R₂, R₃, R₅ are each independently —(CHRCH₂O)_(m)R₄            random copolymer of oxyethylene units and oxypropylene units            where m=10 to 500 and wherein the amount of oxyethylene in            the random copolymer is from about 60% to 100% and the            amount of oxypropylene in the random copolymer is from 0% to            about 40%;        -   R₄=H, Methyl, C₂ to about C₆ Alkyl, or about C₆ to about C₁₀            aryl;        -   M=H, Alkali Metal, Alkaline Earth Metal, Ammonium, Amine,            triethanol amine, Methyl, or C₂ to about C₆ Alkyl;        -   a=0 to about 0.8;        -   b=about 0.2 to about 1.0;        -   c=0 to about 0.5;        -   d=0 to about 0.5; and        -   wherein a, b, c, and d represent the mole fraction of each            unit and the sum of a, b, c, and d is 1.0;    -   h) a dispersant of Formula (IV):        -   wherein in Formula (IV):        -   the “b” structure is one of a carboxylic acid monomer, an            ethylenically unsaturated monomer, or maleic anhydride            wherein an acid anhydride group (—CO—O—CO—) is formed in            place of the groups Y and Z between the carbon atoms to            which the groups Y and Z are bonded respectively, and the            “b” structure must include at least one moiety with a            pendant ester linkage and at least one moiety with a pendant            amide linkage;        -   X=H, CH₃, C₂ to C₆ Alkyl, Phenyl, p-Methyl Phenyl, p-Ethyl            Phenyl, Carboxylated Phenyl, or Sulfonated Phenyl;        -   Y=H, —COOM, —COOH, or W;        -   W=a hydrophobic defoamer represented by the formula            R₅O—(CH₂CH₂O)_(s)—(CH₂C(CH₃)HO)_(t)—(CH₂CH₂O)_(u) where s,            t, and u are integers from 0 to 200 with the proviso that            t>(s+u) and wherein the total amount of hydrophobic defoamer            is present in an amount less than about 10% by weight of the            polycarboxylate dispersant;        -   Z=H, —COOM, —O(CH₂)_(n)OR₃ where n=2 to 6, —COOR₃,            —(CH₂)_(n)OR₃ where n=0 to 6, or —CONHR₃;        -   R₁=H, or CH₃;        -   R₂, R₃, are each independently a random copolymer of            oxyethylene units and oxypropylene units of the general            formula —(CH(R₁)CH₂O)_(m)R₄ where m=10 to 500 and wherein            the amount of oxyethylene in the random copolymer is from            about 60% to 100% and the amount of oxypropylene in the            random copolymer is from 0% to about 40%;        -   R₄=H, Methyl, or C₂ to C₈ Alkyl;        -   R₅=C₁ to C₁₋₈ alkyl or C₆ to C₁₋₈ alkyl aryl;        -   M=Alkali Metal, Alkaline Earth Metal, Ammonia, Amine,            monoethanol amine, diethanol amine, triethanol amine,            morpholine, imidazole;        -   a=0.01-0.8;        -   b=0.2-0.99;        -   c=0-0.5; and        -   wherein a, b, c represent the mole fraction of each unit and            the sum of a, b, and c, is 1;        -   i) a random copolymer corresponding to the following            Formula (V) in free acid or salt form having the following            monomer units and numbers of monomer units:        -   wherein A is selected from the moieties (i) or (ii)        -   wherein R₁ and R₃ are selected from substituted benzene,            C₁₋₈ alkyl, C₂₋₈ alkenyl, C₂₋₈ alkylcarbonyl, C₁₋₈ alkoxy,            carboxyl, hydrogen, and a ring, R₂ and R₄ are selected from            the group consisting of hydrogen and C₁₋₄ alkyl, wherein R₁            and R₃ can together with R₂ and/or R₄ when R₂ and/or R₄ are            C₁₋₄ alkyl form the ring;        -   R₇, R₈, R₉, and R₁₀ are individually selected from the group            consisting of hydrogen, C₁₋₆ alkyl, and a C₂₋₈ hydrocarbon            chain, wherein R₁ and R₃ together with R₇ and/or R₈, R₉, and            R₁₀ form the C₂₋₈ hydrocarbon chain joining the carbon atoms            to which they are attached, the hydrocarbon chain optionally            having at least one anionic group, wherein the at least one            anionic group is optionally sulfonic;        -   M is selected from the group consisting of hydrogen, and the            residue of a hydrophobic polyalkylene glycol or a            polysiloxane, with the proviso that when A is (ii) and M is            the residue of a hydrophobic polyalkylene glycol, M must be            different from the group —(R₅O)_(m)R₆;        -   R₅ is a C₂₋₈ alkylene radical;        -   R₆ is selected from the group consisting of C₁₋₂₀ alkyl,            C₆₋₉ cycloalkyl and phenyl;        -   n, x, and z are numbers from 1 to 100;        -   y is 0 to 100;        -   m is 2 to 1000;        -   the ratio of x to (y+z) is from 1:10 to 10:1 and the ratio            of y:z is from 5:1 to 1:100;    -   j) a copolymer of oxyalkyleneglycol-alkenyl ethers and        unsaturated dicarboxylic acids, comprising:        -   i) 0 to 90 mol % of at least one component of the formula 3a            or 3b:        -   wherein M is a hydrogen atom, a mono- or divalent metal            cation, an ammonium ion or an organic amine residue, a is 1,            or when M is a divalent metal cation a is ½;        -   wherein X is —OM_(a),            -   O—(C_(m)H_(2m)O)_(n)—R¹ in which R¹ is a hydrogen atom,                an aliphatic hydrocarbon radical containing from 1 to 20                carbon atoms, a cycloaliphatic hydrocarbon radical                containing 5 to 8 carbon atoms or an optionally                hydroxyl, carboxyl, C₁₋₁₄ alkyl, or sulphonic                substituted aryl radical containing 6 to 14 carbon                atoms, m is 2 to 4, and n is 0 to 100,            -   —NHR₂, —N(R²)₂ or mixtures thereof in which R²=R¹ or                —CO—NH₂; and        -   wherein Y is an oxygen atom or —NR²;        -   ii) 1 to 89 mol % of components of the general formula 4:        -   wherein R₃ is a hydrogen atom or an aliphatic hydrocarbon            radical containing from 1 to 5 carbon atoms, p is 0 to 3,            and R₁ is hydrogen, an aliphatic hydrocarbon radical            containing from 1 to 20 carbon atoms, a cycloaliphatic            hydrocarbon radical containing 5 to 8 carbon atoms or an            optionally hydroxyl, carboxyl, C₁₋₁₄ alkyl, or sulfonic            substituted aryl radical containing 6 to 14 carbon atoms, m            is 2 to 4, and n is 0 to 100, and        -   iii) 0.1 to 10 mol % of at least one component of the            formula 5a or 5b:        -   wherein S is a hydrogen atom or —COOM_(a) or —COOR₅, T is            —COOR₅, —W—R₇, —CO—[—NH—(CH2)3)—]_(s)—W—R₇,            —CO—O—(CH₂)_(z)—W—R₇, a radical of the general formula:        -   or —(CH₂)_(z)—V—(CH₂)_(z)—CH═CH—R₁, or when S is —COOR₅ or            —COOM_(a), U₁ is —CO—NHM—, —O— or —CH₂O, U₂ is —NH—CO—, —O—            or —OCH₂, V is —O—CO—C₆H₄—CO—O— or —W—, and W is        -   R4 is a hydrogen atom or a methyl radical, R5 is an            aliphatic hydrocarbon radical containing 3 to 20 carbon            atoms, a cycloaliphatic hydrocarbon radical containing 5 to            8 carbon atoms or an aryl radical containing 6 to 14 carbon            atoms, R₆=R₁ or        -   R₇=R₁ or        -   r is 2 to 100, s is 1 or 2, x is 1 to 150, y is 0 to 15 and            z is 0 to 4;        -   iv) 0 to 90 mol % of at least one component of the formula            6a, 6b, or 6c:        -   wherein M is a hydrogen atom, a mono- or divalent metal            cation, an ammonium ion or an organic amine residue, a is 1,            or when M is a divalent metal cation a is ½;        -   wherein X is —OM_(a),            -   —O—(C_(m)H_(2m)O)_(n)—R¹ in which R¹ is a hydrogen atom,                an aliphatic hydrocarbon radical containing from 1 to 20                carbon atoms, a cycloaliphatic hydrocarbon radical                containing 5 to 8 carbon atoms or an optionally                hydroxyl, carboxyl, C₁₋₁₄ alkyl, or sulphonic                substituted aryl radical containing 6 to 14 carbon                atoms, m is 2 to 4, and n is 0 to 100,            -   —NH-(C_(m)H_(2m)O)_(n)—R¹,            -   —NHR₂,—N(R²)₂ or mixtures thereof in which R²=R¹ or                —CO—NH₂; and        -   wherein Y is an oxygen atom or —NR²;    -   k) a copolymer of dicarboxylic acid derivatives and oxyalkylene        glycol-alkenyl ethers, comprising:        -   i) 1 to 90 mol. % of at least one member selected from the            group consisting of structural units of Formula 7a and            Formula 7b:        -   wherein M is H, a monovalent metal cation, a divalent metal            cation, an ammonium ion or an organic amine;        -   a is ½ when M is a divalent metal cation or 1 when M is a            monovalent metal cation;        -   wherein R¹ is —OM_(a), or            -   —O—(C_(m)H_(2m)O)_(n)—R² wherein R² is H, a C₁₋₂₀                aliphatic hydrocarbon, a C₅₋₈ cycloaliphatic                hydrocarbon, or a C₆₋₁₄ aryl that is optionally                substituted with at least one member selected from the                group consisting of [—COOM_(a), —(SO₃)M_(a), and                —(PO₃)M_(a2)];        -   m is 2 to 4;        -   n is 1 to 200;        -   ii) 0.5 to 80 mol. % of the structural units of Formula 8:        -   wherein R³ is H or a C₁₋₅ aliphatic hydrocarbon;        -   p is 0 to 3;        -   R² is H, a C₁₋₂₀ aliphatic hydrocarbon, a C₅₋₈            cycloaliphatic hydrocarbon, or a C₆₋₁₄ aryl that is            optionally substituted with at least one member selected            from the group consisting of [—COOM_(a), —(SO₃)M_(a), and            —(PO₃)M_(a2)];        -   m is 2 to 4;        -   n is 1 to 200;        -   iii) 0.5 to 80 mol. % structural units selected from the            group consisting of Formula 9a and Formula 9b:        -   wherein R⁴ is H, C₁₋₂₀ aliphatic hydrocarbon that is            optionally substituted with at least one hydroxyl group,            —(C_(m)H_(2m)O)_(n)—R², —CO—NH—R², C₅₋₈ cycloaliphatic            hydrocarbon, or a C₆₋₁₄ aryl that is optionally substituted            with at least one member selected from the group consisting            of [—COOM_(a), —(SO₃)M_(a), and —(PO₃)M_(a2)];        -   M is H, a monovalent metal cation, a divalent metal cation,            an ammonium ion or an organic amine;        -   a is ½ when M is a divalent metal cation or 1 when M is a            monovalent metal cation;        -   R² is H, a C₁₋₂₀ aliphatic hydrocarbon, a C₅₋₈            cycloaliphatic hydrocarbon, or a C₆₋₁₄ aryl that is            optionally substituted with at least one member selected            from the group consisting of [—COOM_(a), —(SO₃)M_(a), and            —(PO₃)M_(a2)];        -   m is 2 to 4;        -   n is 1 to 200;        -   iv) 1 to 90 mol. % of structural units of Formula 10        -   wherein R⁵ is methyl, or methylene group, wherein R⁵ forms            one or more 5 to 8 membered rings with R⁷;        -   R⁶ is H, methyl, or ethyl;        -   R⁷ is H, a C₁₋₂₀ aliphatic hydrocarbon, a C₆₋₁₄ aryl that is            optionally substituted with at least one member selected            from the group consisting of [—COOM₃, —(SO₃)M_(a), and            —(PO₃)M_(a2)], a C₅₋₈ cycloaliphatic hydrocarbon, —OCOR⁴,            —OR⁴, or —COOR⁴, wherein R⁴ is H, a C₁₋₂₀ aliphatic            hydrocarbon that is optionally substituted with at least one            —OH, —(C_(m)H_(2m)O)_(n)—R², —CO—NH—R², C₅₋₈ cycloaliphatic            hydrocarbon, or a C₆₋₁₄ aryl residue that is optionally            substituted with a member selected from the group consisting            of [—COOM_(a), —(SO₃)M_(a), —(PO₃)M_(a2)].

In formula (e) the word “de rived” does not refer to derivatives ingeneral, but rather to any polycarboxylic acid/salt side chainderivatives of oligoalkyleneglycols, polyalcohols, polyoxyalkyleneamines, and polyalkylene glycols that are compatible with dispersantproperties and do not destroy the graft polymer.

The preferred substituents in the optionally substituted aryl of formula(j), containing 6 to 14 carbon atoms, are hydroxyl, carboxyl, C₁₋₁₄alkyl, or sulfonate groups.

The preferred substituents in the substituted benzene are hydroxyl,carboxyl, C₁₋₁₄alkyl, or sulfonate groups.

As used herein, the term cement refers to any hydraulic cement.Hydraulic cements are materials which set when mixed with water.Suitable examples of hydraulic cements include, but are not limited to,portland cement, masonry cement, alumina cement, refractory cement,magnesia cement, calcium sulfoaluminate cement, oil well cement, andmixtures thereof.

Pastes are defined as mixtures composed of a hydraulic cement binder,either alone or in combination with pozzolans such as fly ash, silicafume, calcined clay, or blast furnace slag, and water. Mortars aredefined as pastes that additionally include fine aggregate. Concretesadditionally include coarse aggregate.

An amine solubilizing agent can be combined with a water insolubledefoamer and a dispersant for cementitious compositions to form anadmixture for cementitious compositions. The combination of an aminesolubilizing agent with a water insoluble defoamer and a dispersant forcementitious compositions provides an admixture that is stable over timein that there is little or no phase separation between the dispersantand defoamers.

Without being limited to theory, it is theorized that some combinationsof an amine solubilizing agent with a water insoluble defoamer form amicellar solution. A micellar solution is a single, thermodynamicallystable, equilibrium phase; as compared to a macroemulsion, which is adispersion of large droplets, over 200 to 5,000 nanometers, that containtwo or more phases, which are liquids or liquid crystals. Emulsionstypically are opaque, thermodynamically unstable, and macro-dispersesystems of 0.5 to 10 micron droplet size. Micellar solutions aretypically transparent, oil in water systems stabilized by an interfaciallayer of surfactants and have a particle size of about 0.01 to about0.05 microns. The smaller particle size provides for the opticaltransparency. Further definition of micellar solutions can be found inMicroemulsions: Theory and Practice, by L. M. Prince, Academic Press,New York (1977).

Amine solubilizing agents can increase the total aqueous solubilizationof oil in an aqueous phase. When a sufficient amount of solubilizer ispresent in a solution, above the critical micelle concentration, thesolubilizer molecules aggregate into micelles. The micelle-waterpartition coefficient and the molar solubilization ratio cancharacterize the degree of solubility enhancement achieved by an aminesolubilizing agent. The solubilization of the defoamer increases afterthe amine solubilizing agent reaches the critical micelle concentration.The defoamer diffuses through the aqueous phase to the micelles anddissolves in the core of the micelle. As more solubilizer is added, theshape of the micelles will change to cylinder form. As even moresolubilizer is added the shape will eventually change to lamellar.However, the number of micelles will remain about the same throughoutthese changes.

One method of preparing a stable, micellar solution for cementitiouscompositions involves adding an amine solubilizing agent to a mediumcontaining an acid wherein the medium can be water or any solution,mixture, or composition that when containing an acid, forms an acidactivated amine salt, followed by addition of insoluble defoamer whichis solubilized by the amine solubilizing agent, then optionally addingdispersant and any other additives or admixtures.

In another method for producing a stable, micellar solution forcementitious compositions, the amine solubilizing agent, insolubledefoamer, dispersant and any other additives or admixtures can be addedin combination to a medium containing an acid, wherein the medium can bewater or any solution, mixture, or composition that when containing anacid, forms an acid activated amine salt. By “in combination” is meantthe amine solubilizing agent, insoluble defoamer, dispersant and anyother additives or admixtures are added to the acidic medium prior tosolubilizing the defoamer.

The combination of the amine solubilizing agent, insoluble defoamer,dispersant and any other additives or admixtures typically produces astable, transparent micellar solution that has an estimated extendedstability of several years. Additionally, in the alkaline pH environmentof the cementitious composition, the amine solubilizing agent isinactivated to the unprotonated (non-salt) form, and greater defoamingperformance is observed.

An activated amine solubilizing agent refers to an amine surfactant thathas been reacted with an acid to form a water soluble salt. Adeactivated amine solubilizing agent refers to an amine surfactant whichis in the unprotonated (non-salt) form.

Examples of the amine solubilizing agents include, but are not limitedto, (mono, di, tri) alkyl amine, (mono, di, tri) alkyl ether amine,alkoxylated amine, alkyl amide amine, alkylimidazoline, alkyl (di ortri,) amine, alkyl (di or tri) ether amine, alkoxylated (di or tri)amine, ethoxylated alkyl ether amine, or mixtures thereof.

In one embodiment the ether amines are DA-series ether diamines fromTomah Products, Inc., Milton Wis. and comprise the following formula:R—O—CH₂CH₂CH₂NHCH₂CH₂CH₂NH₂. In another embodiment the ether amines havethe following formulas: DA-1214 has R as C₈H₁₇/C₁₀H₂₁(Octyl/decyloxypropyl-1,3-diaminopropane; DA-14 has R as Branched C₁₀H₂₁(Isodecyloxypropyl-1,3-diaminopropane); DA-16 has R as Branched C₁₂H₂₅(Isododecyloxypropyl-1,3-diaminopropane); DA-1618 has R as C₁₂H₂₅/C₁₄H₂₉(Dodecyl/tetradecyloxypropyl-1,3-diaminopropane); DA-17 has R asBranched C₁₃H₂₇ (Isotridecyloxypropyl-1,3-diaminopropane); and DA-18 hasR as C₁₄H₂₉ (Tetradecyloxypropyl-1,3-diaminopropane).

In one embodiment the ether amines are PA-series primary ether diamines(ethoxylated alkyl diamine and alkyl diamine) from Tomah Products, Inc.,Milton Wis. In certain embodiments the primary ether amines have thefollowing formulas: PA-7 has R as Iso C₃H₇ (isopropyloxypropyl amine);PA-10 has R as Branched C₆H₁₃ (Isohexyloxypropyl amine); PA-12 EH has Ras Branched C₆H₁₃ (2-ethylhexyloxypropyl amine); PA-1214 has R asC₈H₁₇/C₁₀H₂₁ (Octyl/decyloxypropyl amine); PA-14 has R as BranchedC₁₀H₂₁ (Isodecyloxypropyl amine); PA-16 has R as Branched C₁₂H₂₅(Isododecyloxypropyl amine); PA-1618 has R as C₈H₁₇/C₁₀H₂₁(Dodecyl/tetradecyloxypropyl amine); PA-17 has R as Branched C₁₃H₂₇(Isotridecyloxypropyl amine); PA-18 has R as C₁₄H₂₉ (Tetradecyloxypropylamine); PA-1816 has R as C₁₄H₂₉/C₁₂H₂₅ (Tetradecyl/dodecyloxypropylamine); PA-19 has R as C₁₂H₂₅/C₁₅H₃₁ (Linear alkyloxypropyl amine); andPA-2220 has R as C₁₈H₃₇/C₁₆H₃₃ (Octadecyl/hexadecyloxypropyl amine).

In one embodiment the ethoxylated ether amines are E-series ethoxylatedether amines from Tomah Products, Inc., Milton Wis. and comprise thefollowing formula:

In certain embodiments the ethoxylated ether amines have the followingformulas: E-14-2 has R as Branched C₁₀H₂₁ (iso-(2-hydroxyethyl)isodecyloxypropylamine); E-14-5 has R as Branched C₁₀H₂₁ (poly (5)oxyethylene isodecyloxypropylamine); E-17-2 has R as Branched C₁₃H₂₇(bis-(2-hydroxyethyl) isotridecyloxypropylamine); E17-5 has R asBranched C₁₃H₂₇ (poly (5) oxyethylene isotridecyloxypropylamine); E19-2has R as C₁₂H₂₅/C₁₅H₃₁ (bis-(2-hydroxyethyl) linear C12-15alkyloxypropylamine); E-22-2, E-2220-2 and E-18-2 has R as C₁₈H₂₇(bis-(2-hydroxyethyl) octadecylamine (&5, 15 mole adduct)); E-S-2 has Ras Oleic/Linoleic (bis-(2-hydroxyethyl) soya amine (&15 mole adduct));E-T-2 has R as Stearic/Oleic (bis-(2-hydroxyethyl) tallow amine (&5, 15mole adduct)).

In one embodiment the amine solubilizing agent has a molecular weight ofabout 100 to about 1000.

Illustrative examples of amine solubilizing agents capable ofcontrolling the air content in cementitious compositions that can beused are di coco alkylamine, tridodecyl amine, oleyl dimethyl amine,hydrogenated tallow dimethyl amine, oleyl amine, tallow amine, dodecylether amine or tetradecyl ether amine, ethoxylated(2)cocoalkyl amine,propoxylated(2)tallowalkyl amine, bis (2-hydroxyethyl)oleyl amine, bis(2-hydroxyethyl)octadecyl amine, polyoxyethylene(15)tallowalkyl amine,bis (2-hydroxyethyl)cocoalkyl amine or N-oleyl-1,1-iminobis-2-propanol,lauramidopropyl dimethylamine, stearamidopropyl dimethylamine oroleamidopropyl dimethylamine,1-(2-hydroxyethyl)-2-(heptadecenyl)imidazoline, oleylhydroxyethylimidazoline, or cocoalkyl hydroxyethyl imididazoline, oleyldiamine, tallow pentamine, tallow tetramine, tallow triamine,N-oleyl-1,3-diaminopropane,tris(2-hydroxyethyl)-N-tallowalkyl-1,3-diaminopropane, isotridecyloxypropyl-1,3-diaminopropane or tetradecyloxypropyl-1,3-diaminopropane,ethoxylated(3)N-tallow-1,3-diaminopropane, and mixtures thereof.

“Solubilized” refers to the aggregation or self assembly micellizationof surfactant in water in which a water insoluble species resides andparticle sizes are small enough to provide optical transparency.“Soluble” refers to the interaction of an individual molecule withwater.

Amine solubilizing agents according to the present invention preferablyare at least partially effective themselves as defoamers forcementitious compositions. But, the combination of amine solubilizingagents and insoluble defoamers provide increased air control incementitious mixtures over use of amine solubilizing agents alone.

The amount of the dispersant for cementitious compositions that ispresent in the admixture ranges from about 0 to about 60% based on theweight of dry solids. The amount of the dispersant for cementitiouscompositions that is present in a cementitious mixture ranges from about0% to about 2.0% primary active ingredient based on the dry weight ofcementitious material. Preferably, the amount of dispersant forcementitious compositions that is present in a cementitious mixtureranges from about 0.05% to about 0.5% primary active ingredient based onthe dry weight of cementitious material.

The amount of amine solubilizing agent that is present in the admixtureis at least the amount sufficient to obtain a stable solution.Preferably the amount of amine solubilizing agent that is present in theadmixture is from about 0.02% to about 60% based on the weight of drysolids. Preferably the amount of amine solubilizing agent that ispresent in a cementitious mixture ranges from about 0.0001% to about0.2% primary active ingredient based on the dry weight of cementitiousmaterial.

The amount of water insoluble defoamer that is present in the admixtureranges from about 0.02% to about 30% based on weight of dry solids.Preferably, the amount of water insoluble defoamer that is present inthe admixture ranges from about 0.25% to about 10% based on weight ofdry solids. Preferably the amount of water insoluble defoamer that ispresent in a cementitious mixture ranges from about 0.0001% to about0.1% primary active ingredient based on the dry weight of cementitiousmaterial.

The amount of acid that is present in the admixture is at least theamount sufficient to form an acid activated water soluble amine salt.Preferably the amount of acid that is present in the admixture is from 0to about 25% based on the weight of dry solids. Preferably the amount ofacid that is present in a cementitious mixture ranges from 0 to about 2%primary active ingredient based on the dry weight of cementitiousmaterial. In some embodiments the acidic medium used to form an acidactivated water soluble amine salt is provided by dispersants.

The weight ratio of amine solubilizing agent to insoluble defoamerranges from about 0.25:1 to about 5:1.

Examples of water insoluble defoamers useful to control the air contentin cementitious compositions include, but are not limited to, chemicalsbased on mineral or vegetable oils, fats and oils, fatty acid esters,any chemical with —OH (hydroxyl) functionality (such as alcohols,particularly fatty alcohols), ether compounds, phosphoric esters,silicones, polyoxyalkylenes, polymers comprising ethylene oxide and/orpropylene oxide moieties, liquid hydrocarbons, and acetylenic compounds.

Suitable examples of the water insoluble defoamers useful to control theair content in cementitious compositions include DYNOL™ 604, SURFYNOL®440, SURFYNOL® 104, SURFYNOL® 2502, SURFYNOL® 420, SURFYNOL® DF-75,nonyl phenol, ethoxylated nonyl phenol, tributyl phosphate, triisobutylphosphate, and polypropylene oxide.

Further examples of water insoluble defoamers include the following:kerosene, liquid paraffin, animal oil, vegetable oil, sesame oil, castoroil, alkylene oxide adducts thereof, natural wax, linear or branchedfatty alcohols and their alkoxylated derivatives, octyl alcohol,hexadecyl alcohol, acetylene alcohol, acetylinic alcohol alkoxylates,glycols, polyoxyalkylene glycol, polyoxyalkylene amide, acrylatepolyamine, silicone oil, silicone paste, silicone emulsion, organicmodified polysiloxane, fluorosilicone oil; and polyoxyethylenepolyoxypropylene adducts. To the extent that the defoamers in thepreceding list contain alkylene oxides, reference is made to those(longer chain polyalkylene oxides) that are water insoluble.

Elevated temperature stability for any combination of insoluble defoamerand dispersant for cementitious compositions can be obtained byincreasing the level of the amine solubilizing agent or reducing theamount of insoluble defoamer. For example, depending upon the insolubledefoamer level and the effectiveness of the amine solubilizing agent, atemperature increase from 25° C. to 45° C. may possibly need a 10-20%increase in the amount of amine solubilizing agent to maintain a stablesolution.

The admixture of the present invention can be used in combination withany other admixture or additive for cement. Other cement admixtures andadditives include, but are not limited to, set retarders, setaccelerators, air-entraining or air detraining agents, corrosioninhibitors, any other dispersants for cement, pigments, wetting agents,water soluble polymers, strength enhancing agents, rheology modifyingagents, water repellents, and any other admixture or additive that doesnot adversely affect the properties of the admixture of the presentinvention.

Other dispersants for cement include, but are not limited to, calciumlignosulfonates, beta naphthalene sulfonates, sulfonated melamineformaldehyde condensates, any other chemical that functions as adispersant or water reducer or superplasticizer for cement, and mixturesthereof.

Listed below are several examples of admixtures and additives that canbe used with the present invention. U.S. Pat. No. 5,728,209 to Bury etal., which is incorporated herein by reference, contains a detaileddescription of different types of admixtures.

The term air entrainer includes any chemical that will entrain air incementitious compositions. Air entrainers can also reduce the surfacetension of a composition at low concentration. Air-entraining admixturesare used to purposely entrain microscopic air bubbles into concrete.Air-entrainment dramatically improves the durability of concrete exposedto moisture during cycles of freezing and thawing. In addition,entrained air greatly improves a concrete's resistance to surfacescaling caused by chemical deicers. Air entrainment also increases theworkability of fresh concrete while eliminating or reducing segregationand bleeding. Materials used to achieve these desired effects can beselected from salts of wood resin; (Vinsol resin); some syntheticdetergents; salts of sulfonated lignin; salts of petroleum acids; saltsof proteinaceous material; fatty and resinous acids and their salts;alkylbenzene sulfonates; and salts of sulfonated hydrocarbons. Airentrainers are added in an amount to yield a desired level of air in acementitious composition. Generally, the amount of air entrainers in acementitious composition ranges from about 0.2 to about 5.0 fluid ouncesper hundred pounds of cementitious material. But this can vary widelydue to variations in materials, mix proportion, temperature, and mixingaction.

Retarding, or delayed-setting, admixtures are used to retard, delay, orslow the rate of setting of concrete. They can be added to the concretemix upon initial batching or sometime after the hydration process hasbegun. Retarders are used to offset the accelerating effect of hotweather on the setting of concrete, or delay the initial set of concreteor grout when difficult conditions of placement occur, or problems ofdelivery to the job site, or to allow time for special finishingprocesses or to aid in the reclamation of concrete left over at the endof the work day. Most retarders also act as water reducers and can alsobe used to entrain some air into concrete. The retarder used in theadmixture of the present invention can include, but is not limited to anoxy-boron compound, lignin, a polyphosphonic acid, a carboxylic acid, ahydroxycarboxylic acid, polycarboxylic acid, hydroxylated carboxylicacid, fumaric, itaconic, malonic, borax, gluconic, and tartaric acid,lignosulfonates, ascorbic acid, isoascorbic acid, sulphonic acid-acrylicacid copolymer, and their corresponding salts, polyhydroxysilane,polyacrylamide, carbohydrates and mixtures thereof. Illustrativeexamples of retarders are set forth in U.S. Pat. Nos. 5,427,617 and5,203,919, incorporated herein by reference. A further example of aretarder particularly suited for use in the present invention is ahydration control admixture sold under the trademark DELVO® by MasterBuilders Inc. of Cleveland, Ohio.

Air detrainers are used to decrease the air content in the mixture ofconcrete. Dibutyl phthalate, octyl alcohol, water-insoluble esters ofcarbonic and boric acid, and silicones are some of the common materialsthat can be used to achieve this effect.

Alkali-reactivity reducers can reduce the alkali-aggregate reaction andlimit the disruptive expansion forces in hardened concrete. Pozzolans(fly ash, silica fume), blast-furnace slag, salts of lithium and bariumare especially effective.

Bonding admixtures are usually added to portland cement mixtures toincrease the bond strength between old and new concrete and includeorganic materials such as rubber, polyvinyl chloride, polyvinyl acetate,acrylics, styrene butadiene copolymers, and other powdered polymers.

Water-reducing admixtures are used to reduce the amount of mixing waterrequired to produce concrete of a certain slump, to reduce the ratio ofwater and cementitious material, or to increase slump. Typically, waterreducers will reduce the water content of the concrete mixture byapproximately up to 15%.

Superplasticizers are high-range water reducers, or water-reducingadmixtures. They are added to concrete to make high-slump, flowingconcrete, and thus reduce the water-cementitious material ratio. Theseadmixtures produce large water reduction or great flowability withoutcausing undue set retardation or entrainment of air in mortar orconcrete. Among the materials that can be used as superplasticizers aresulfonated melamine formaldehyde condensates, sulfonated naphthaleneformaldehyde condensates, certain organic acids, lignosulfonates, and/orblends thereof.

Natural and synthetic admixtures are used to color concrete foraesthetic and safety reasons. These coloring admixtures are usuallycomposed of pigments and include carbon black, iron oxide,phthalocyanine, umber, chromium oxide, titanium oxide and cobalt blue.

Corrosion inhibitors in concrete serve to protect embedded reinforcingsteel from corrosion due to its highly alkaline nature. The highalkaline nature of the concrete causes a passive and noncorrodingprotective oxide film to form on the steel. However, carbonation or thepresence of chloride ions from deicers or seawater can destroy orpenetrate the film and result in corrosion. Corrosion-inhibitingadmixtures chemically arrest this corrosion reaction. The materials mostcommonly used to inhibit corrosion are calcium nitrite, sodium nitrite,sodium benzoate, certain phosphates or fluorosilicates,fluoroaluminates, amines, organic based water repelling agents, andrelated chemicals.

Dampproofing admixtures reduce the permeability of concrete that havelow cement contents, high water-cementitious material ratios, or adeficiency of fines in the aggregate. These admixtures retard moisturepenetration into dry concrete and include certain soaps, stearates, andpetroleum products.

Grouting agents, such as air-entraining admixtures, accelerators,retarders, and non-shrink and workability agents, adjust groutproperties to achieve a desired result for specific applications. Forexample, portland cement grouts are used for a variety of differentpurposes, each of which may require a different agent to stabilizefoundations, set machine bases, fill cracks and joints in concrete work,cement oil wells, fill cores of masonry walls, grout pre-stressingtendons and anchor bolts, or fill the voids in pre-placed aggregateconcrete.

Gas formers, or gas-forming agents, are sometimes added to concrete andgrout in very small quantities to cause a slight expansion prior tohardening. The amount of expansion is dependent upon the amount ofgas-forming material used and the temperature of the fresh mixture.Aluminum powder, resin soap and vegetable or animal glue, saponin orhydrolyzed protein can be used as gas formers.

Permeability reducers are used to reduce the rate at which water underpressure is transmitted through concrete. Silica fume, fly ash, groundslag, natural pozzolans, water reducers, and latex can be employed todecrease the permeability of the concrete. Pozzolan is a siliceous orsiliceous and aluminous material, which in itself possesses little or nocementitious value. However, in finely divided form and in the presenceof moisture, pozzolan will chemically react with calcium hydroxide atordinary temperatures to form compounds possessing cementitiousproperties.

Pumping aids are added to concrete mixes to improve pumpability. Theseadmixtures thicken the fluid concrete, i.e., increase its viscosity, toreduce de-watering of the paste while it is under pressure from thepump. Among the materials used as pumping aids in concrete are organicand synthetic polymers, hydroxyethylcellulose (HEC) or HEC blended withdispersants, organic flocculents, organic emulsions of paraffin, coaltar, asphalt, acrylics, bentonite and pyrogenic silicas, naturalpozzolans, fly ash and hydrated lime.

Bacteria and fungal growth on or in hardened concrete may be partiallycontrolled through the use of fungicidal, germicidal, and insecticidaladmixtures. The most effective materials for these purposes arepolyhalogenated phenols, dialdrin emulsions, and copper compounds.

Fresh concrete can sometimes be harsh because of faulty mixtureproportions or certain aggregate characteristics such as particle shapeand improper grading. Under these conditions, entrained air which actslike a lubricant, can be used as a workability improving agent. Otherworkability agents are water reducers and certain finely dividedadmixtures.

Finely divided mineral admixtures are materials in powder or pulverizedform added to concrete before or during the mixing process to improve orchange some of the plastic or hardened properties of portland cementconcrete. Portland cement, as used in the trade, means a hydrauliccement produced by pulverizing clinker, consisting essentially ofhydraulic calcium silicates, all usually containing one or more of theforms of calcium sulfate as an interground addition with ASTM types, I,II, III, IV, or V. The finely divided mineral admixtures can beclassified according to their chemical or physical properties as:cementitious materials; such as pozzolans; pozzolanic and cementitiousmaterials; and nominally inert materials. Cementitious materials arematerials that alone have hydraulic cementing properties, and set andharden in the presence of water. Included in cementitious materials areground granulated blast-furnace slag, natural cement, hydraulic hydratedlime, and combinations of these and other materials. As discussed above,pozzolan is a siliceous or aluminosiliceous material that possesseslittle or no cementitious value but will, in the presence of water andin finely divided form, chemically react with the calcium hydroxidereleased by the hydration of portland cement to form materials withcementitious properties. Diatomaceous earth, opaline cherts, clays,shales, fly ash, silica fume, volcanic tuffs and pumicites are some ofthe known pozzolans. Certain ground granulated blast-furnace slags andhigh calcium fly ashes possess both pozzolanic and cementitiousproperties. Natural pozzolan is a term of art used to define thepozzolans that occur in nature, such as volcanic tuffs, pumices,trasses, diatomaceous earths, opaline, cherts, and some shales.Nominally inert materials can also include finely divided raw quartz,dolomites, limestones, marble, granite, and others. Fly ash is definedin ASTM C-618.

In the construction field, many methods of strengthening concrete havebeen developed through the years. One modem method involves distributingfibers throughout a fresh concrete mixture. Upon hardening, thisconcrete is referred to as fiber-reinforced concrete. Fibers can be madeof zirconium materials, steel, fiberglass, or synthetic materials, e.g.,polypropylene, nylon, polyethylene, polyester, rayon, high-strengtharamid, (i.e. KEVLAR®), or mixtures thereof.

A cementitious composition having controlled air content can be formedwhich comprises cementitious material, water, a water insolubledefoamer, a dispersant for cementitious compositions, and an aminesolubilizing agent that solubilizes the water insoluble defoamer. Thecementitious material can include fine aggregates, coarse aggregates,pozzolans, air (either entrapped or purposefully entrained), calcinedclay, and pigments.

The fine aggregates are materials that pass through a Number 4 sieve(ASTM C125 and ASTM C33), such as natural or manufactured sand. Thecoarse aggregates are materials that are retained on a Number 4 sieve(ASTM C125 and ASTM C33), such as silica, quartz, crushed round marble,glass spheres, granite, limestone, calcite, feldspar, alluvial sands, orany other durable aggregate, and mixtures thereof.

A method of controlling air in a cementitious composition is alsoprovided according to the present invention which comprises mixingcementitious material, water, a water insoluble defoamer, an aminesolubilizing agent that solubilizes the water insoluble defoamer, andoptionally a dispersant for cementitious compositions. Other admixturesand additives are added to the cementitious composition at appropriatetimes prior or subsequent to the addition of the inventive admixture.

The amount of water added to the cementitious composition is calculatedbased on the desired water to cementitious material (W/C) ratio. Thewater to cementitious material ratio typically ranges from about 0.2 toabout 0.7 with the water and cementitious material being measured byweight.

SPECIFIC EMBODIMENTS OF THE INVENTION

Samples of micellar solutions and cementitious compositions wereprepared using different insoluble defoamers, solubilizing agents, acidsand dispersants for cementitious compositions. The cementitiouscompositions additionally contained cement and aggregate. The dispersantfor cementitious compositions used in the following examples was apolycarboxylate dispersant, which was a polymer with polymericcarboxylate backbone with polyether side chains.

The following tests were used: Slump (ASTM C143) and Aircontent-volumetric (ASTM C231). Aggregates met the specifications ofASTM C33. The term W/C refers to the water to cementitious materialratio in a cementitious mixture. The term S/A refers to the sand toaggregate ratio by volume.

Solution Samples

To determine which amines would function as solubilizing agents,solutions were prepared that comprised water, an insoluble defoamer,amine solubilizing agent, acid, and optionally polycarboxylatedispersant, shown below in Tables 1 and 2. The amounts of the materialsare shown as percent by weight of the solution. The solutions wereprepared initially by combining water, acid, amine solubilizing agent,insoluble defoamer, and optionally polycarboxylate dispersant (Table 2),with continuous stirring with a magnetic stir bar in a glass beaker.Another method of preparation involved adding all of the components tothe beaker at the same time and stirring until a clear solution wasobtained.

Samples S1-S51 were prepared as described above with all samplescomprising from 3 to 8% insoluble defoamer, an amine solubilizing agent,sufficient acid to render the amine solubilizing agent active, and nopolycarboxylate dispersant.

TABLE 1 Sample Def. % ASA/Def. Acid Solution Stability # Def. by wt. ASAby wt. Acid % by wt. Appearance (at X days) S1 PO 1000 6 Oleyl Amine 2EO2:1 acetic 2.60 clear stable @ 148 S2 PO 2000 6 Oleyl Amine 2EO 2:1acetic 2.60 clear stable @ 148 S3 PO 2000 6 Tallow Amine 2EO 1.5:1acetic 1.20 clear stable @ 98 S4 PO 2000 6 Tallow Amine 5EO 1.5:1 acetic1.20 cloudy stable @ 98 S5 S-420 6 Tallow Amine 2EO 1.5:1 acetic 2.40clear stable @ 96 S6 S-420 6 Tallow Amine 5EO 1.5:1 acetic 1.20 clearstable @ 96 S7 S-420 6 Tallow Amine 5EO 1.25:1 acetic 1.00 clear stable@ 96 S8 S-420 6 Oleyl Amine 2EO 1.5:1 acetic 1.95 clear stable @ 96 S9S-420 4 1-hydroxyethyl-2- 1:1 acetic 2.00 clear stable @ 96 tall oilalkylimidazoline S10 S-440 6 Tallow Amine 2EO 1.5:1 acetic 2.40 clearstable @ 98 S11 S-440 6 Tallow Amine 5EO 1.25:1 acetic 1.00 clear stable@ 98 S12 S-440 6 Oleyl Amine 2EO 1.5:1 acetic 1.95 clear stable @ 98 S13TBP 4 Tallow Amine 5EO 3:1 gluconic 8.00 clear stable @ 175 S14 TBP 8Oleyl Amine 2EO 1.5:1 acetic 2.60 clear stable @ 169 S15 TBP 4 TallowAmine 5EO 3:1 acetic 1.60 clear S16 TBP 6 Oleyl Amine 2EO 2:1 acetic2.60 clear stable @ 147 S17 TBP 6 Olcyl Amine 2EO 2.5:1 acetic 3.25clear stable @ 152 S18 TBP 6 oleamidopropyl 2:1 acetic 2.60 clear stable@ 148 dimethyl amine S19 TBP 4.286 oleamidopropyl 2.5:1 acetic 2.32clear stable @ 147 dimethyl amine S20 TBP 4 Tallow Amine 5EO 2:1 acetic1.07 clear stable @ 148 S21 TBP 3.967 Tallow Amine 2EO 2:1 acetic 2.02clear stable @ 147 S22 TBP 3.94 Tallow Amine 2EO 3:1 acetic 3.27 clearstable @ 147 S23 TBP 4 Tallow Amine 2EO 1.5:1 Acetic 1.65 clear stable @70 S24 TBP 49 Tallow Amine 2EO + 3:1 acetic 3.30 clear stable @ 124Tallow Amine 5EO S25 TBP 4 Tallow Amine 2EO + 3:1 acetic 3.30 clearstable @ 140 Tallow Amine 5EO S26 TBP 4 Tallow Amine 2EO 3.5:1 acetic3.91 clear stable @ 107 S27 TBP 4 Tallow Amine 2EO 4:1 acetic 4.47 clearstable @ 107 S28 TBP 4 Tallow Amine 2EO 1.75:1 acetic 1.93 clear stable@ 90 S29 TBP 4 Tallow Amine 5EO 1.75:1 acetic 0.94 clear stable @ 89 S30TBP 8 oleamidopropyl 1.5:1 acetic 2.60 clear dimethyl amine S31 TBP 4Tallow Amine 5EO 1.5:1 acetic 1 Cloudy S32 TBP 6 Tallow Amine 5EO 2:1Acetic 1.61 clear stable @ 137 S33 TBP 4 Tallow Amine 15EO 1.5.1 acetic1 Cloudy S34 TBP 4 Tallow Amine 15EO 2.5:1 acetic 1 Clear S35 TBP 3Tallow Triamine 3:1 acetic 6.00 clear stable @ 63 S36 TBP 4 Tallow Amine2EO 1.5:1 acetic 2.40 clear stable @ 96 S37 TBP 4 None — — — Cloudy/SepS38 TBP 4 Oleyl Amine 2EO 1.5:1 acetic 1 Clear S39 TBP 4 Tallow Amine2EO 1.5.1 acetic 1 Clear S40 TBP 4 Tallow Amine 2PO 1.5.1 acetic 1 ClearS41 TBP 4 1-hydroxyethyl-2- 1.5: acetic 1 Clear oleylimidazoline S42 TBP4 1-hydroxyethyl-2- 1.5:1 acetic 1 Clear cocoimidazoline S43 TBP 4oleamidopropyl 1.5:1 acetic 1 Clear dimethyl amine S44 TBP 4stearamidopropyl 1.5:1 acetic 1 Clear dimethyl amine S45 TBP 4lauramidopropyl 1.5:1 acetic 1 Clear dimethyl amine S46 S-440 5 OleylAmine 2EO 1.5:1 acetic 1 Clear stable > 30 S47 TBP 5 Oleyl Amine 2EO1.5:1 acetic 1 Clear stable > 30 S48 Surfynol 5 Oleyl Amine 2EO 1.5:1acetic 1 Clear stable > 30 104H S49 S- 5 Oleyl Amine 2EO 1.5:1 acetic 1Clear stable > 30 420 S50 S- 5 Oleyl Amine 2EO 1.5:1 acetic 1 Clearstable > 30 2502 S51 D-604 5 Oleyl Amine 2EO 1.5:1 acetic 1 Clearstable > 30 ASA = amine solubilizing agent Def = defoamer TBP =tributylphosphate TIBP = Triisobutyl phosphate S-440 = Surfynol 440S-420 = Surfynol 440 S-2502 = Surfynol 2502 D-604 = Dynol 604 PO-1000 =polypropylene glycol mw1000 PO-2000 = polypropylene glycol mw2000

Samples S1-3, S5-30, S32, S34-36, and S38-51 show that stable micellarsolutions were produced by using various amine solubilizing agents incombination with different insoluble defoamers. The cloudy solution ofthe control (S37) which did not have an amine solubilizing agentdemonstrates that the insoluble defoamer was not stabilized andseparation was immediate. Comparison of samples S31 and S33 versus S32and S34 shows that the ratio of amine solubilizing agent to insolubledefoamer can be optimized in order to obtain a stable solution.

Samples S52-S73 were prepared as described above with all samplescomprising one of four different polycarboxylate dispersants (PC-1,2 & 3are polymers having shorter (lower molecular weight) PEG side chains anddifferent charge densities and PC-4 has longer PEG side chains), 0.1 to1.6% insoluble defoamer by weight of solution, amine solubilizing agent,and sufficient acid to render the amine solubilizing agent active.

TABLE 2 Sample Disp. % Def. % ASA/Def Acid % Solution Stability # Disp.by wt. Def. by wt. ASA by wt. Acid by wt. Appearance (at X days) S52PC-1 20 TBP 1.00 Dodecyl Amine 2:1 acetic 1 Clear stable > 30 S53 PC-120 TBP 1.00 Oleyl Amine 2:1 acetic 1 Clear stable > 30 S54 PC-1 20 TBP1.00 Oleyl Amine 2EO 2:1 acetic 1 Clear stable > 30 S55 PC-1 20 TBP 1.00Steayl Amine 2EO 2:1 acetic 1 Clear stable > 30 S56 PC-1 20 TBP 1.00Tallow Amine 2EO 2:1 acetic 1 Clear stable > 30 S57 PC-1 20 TBP 1.00Tallow Amine 5EO 2:1 acetic 1 Clear stable > 30 S58 PC-2 20 S-440 0.10None 0 None 0 Clear stable > 30 S59 PC-2 20 S-440 0.20 None 0 None 0Clear stable > 30 S60 PC-2 20 S-440 0.40 Oleyl Amine 2EO 1.5:1 acetic 5Clear stable > 30 S61 PC-2 20 S-440 0.40 Dodecydimethylmaine 1.5:1acetic 0 Clear stable > 30 S62 PC-2 20 S-440 0.60 Oleyl Amine 2EO 1.5:1acetic 5 Clear stable > 30 S63 P0-2 20 S-440 0.80 Oleyl Amine 2EO 1.5:1acetic 5 Clear stable > 30 S64 PC-2 20 S-440 1.00 Oleyl Amine 2EO 1.5:1acetic 5 Clear stable > 30 S65 PC-2 20 S-440 1.60 Oleyl Amine 2EO 1.5:1acetic 5 Clear stable > 30 S66 PC-2 20 75% S- 0.80 Oleyl Amine 2EO 1.5:1acetic 6.6 Clear stable > 30 440 + 25% TBP S67 PC-2 20 98% S- 1.02 OleylAmine 2EO 1.5:1 acetic 6.6 Clear stable > 30 440 + 2% TBP S68 PC-2 2095% S- 1.05 Oleyl Amine 2EO 1.5:1 acetic 6.6 Clear stable > 30 440 + 5%TBP S69 PC-2 20 91% S- 1.10 Oleyl Amine 2EO 1.5:1 acetic 6.6 Clearstable > 30 440 + 9% TBP S70 PC-2 20 91% 5- 1.10 Oleyl Amine 2EO 1.5:1acetic 6.6 Clear stable > 30 440 + 9% TBP S71 PC-1 25 TBP 1.00 Hexadecyl2:1 acetic 0.8 Clear stable > 30 dimethylamine S72 PC-3 25 TBP 1.00Oleyl Amine 2EO 1.5:1 acetic 0.6 Cloudy stable @ 140 S73 PC-4 20 S-4400.20 Oleyl Amine 2EO 1.5:1 acetic 0.5 Cloudy stable @ 15 ASA = aminesolubilizing agent Disp. = dispersant Def = defoamer TBP =tributylphosphate S-440 = Surfynol 440

Samples S52-S73 illustrate that, in the presence of differentpolycarboxylate dispersants, various amines solubilized an insolubledefoamer in an acidic medium to form a stable, transparent solution.While solution clarity is preferable for indicating the best long-termsolution stability, the nature of the polycarboxylate dispersant caninfluence solution clarity. However, cloudy solutions with adequatestability can also be obtained using the amine solubilizing agents asdemonstrated by Samples S72 and S73.

Samples in Table 3 were prepared as described above with all samplescomprising 20% polycarboxylate dispersant. The insoluble defoamer usedwas the commercially available product S-440 (SURFYNOL® 440) from AirProducts and Chemicals, Allentown, Pa. which is a 40% ethylene oxideadduct to 2,4,7,9-tetramethyl-5-decyne-4,7-diol.

TABLE 3 Def % ASA/Def Acid % Solution Sample Def (by wt) ASA (by wt)Acid (by wt) Appearance S58 S-440 0.10 None 0 None 0 Clear S59 S-4400.20 None 0 None 0 Clear S74 S-440 1.00 None 0 None 0 Cloudy S75 S-4400.40 Oleyl Amine 2EO 1.5:1 Acetic 1 Hazy S76 S-440 0.60 Oleyl Amine 2EO1.5:1 Acetic 1 Hazy S77 S-440 0.80 Oleyl Amine 2EO 1.5:1 Acetic 1 HazyS78 S-440 1.00 Oleyl Amine 2EO 1.5:1 Acetic 1 Hazy S79 S-440 1.60 OleylAmine 2EO 1.5:1 Acetic 1 Hazy S60 S-440 0.40 Oleyl Amine 2EO 1.5:1Acetic 5 Clear S62 S-440 0.60 Oleyl Amine 2EO 1.5:1 Acetic 5 Clear S63S-440 0.80 Oleyl Amine 2EO 1.5:1 Acetic 5 Clear S64 S-440 1.00 OleylAmine 2EO 1.5:1 Acetic 5 Clear S65 S-440 1.60 Oleyl Amine 2EO 1.5:1Acetic 5 Clear S-440 = SURFYNOL ® 440 ASA = amine solubilizing agent Def= defoamer

The Samples in Table 3 illustrate that in solutions without solubilizingagents, increasing amounts of insoluble defoamer (above 0.20%) made thesolution cloudy (S74) due to the separate phase created by theunsolubilzed defoamer. The results show that by increasing the amount ofacid in solution, a typical stable transparent mixture is obtainedwithout further increases in amine solubilizing agent. This isdemonstrated by samples S60-S64 which solubilized the insoluble defoamerand had the same amounts of surfactant and defoamer as samples S75-S79,but had a greater amount of acid (5% compared to 1% by weight).

Concrete Performance Examples

The concrete mixture proportions for the examples shown in Tables 4-8were based on a 600 lb/yd³ cement factor mixture using Type I portlandcement, a sand to aggregate (S/A) ratio of 0.42 to 0.45 using limestonecoarse aggregate and natural sand, and a water to cement (W/C) ratio of0.4 to 0.5. All of the values shown are expressed as percent activematerial by cement weight in the concrete mixture.

Tables 4 and 5 show the performance of various amine solubilizing agentsover a concrete temperature range of 50-70° F., with and withoutadditional defoamer, in cementitious mixtures containing apolycarboxylate dispersant. The mixtures in Table 4 do not contain anair-entraining agent, the mixtures in Table 5 were air-entrained using acommercially available, proprietary product, Micro-Air® admixture,manufactured by Master Builders, Inc. Cleveland, Ohio. The aminesolubilizing agent dosage was fixed at 0.0091% by cement weight and thedefoamer dosage, when used, was 0.0061% by cement weight resulting in anamine solubilizing agent (ASA) to defoamer ratio of 1.5:1. In theseexamples, each component was added separately to the cementitiousmixture at the beginning of the mix sequence.

Table 6 shows air-entrained mixtures using Micro-Air admixture and a lowdose of polycarboxylate dispersant comparing the addition of onlydefoamer, at 0.0032% by weight based on the weight of cement, to that ofa combination of amine solubilizing agent and defoamer at a 1:1 ratio.In these examples, each component was added separately to thecementitious mixture at the beginning of the mix sequence.

TABLE 4 Sample S80 S81 S82 S83 S84 S85 S86 S87 S88 S89 ASA None OleylOleyl Decyl Decyl None Oleyl Oleyl Tallow Tallow Amine Amine Amine AmineAmine Amine Amine Amine 2EO 2EO 2EO 2EO 2EO 2EO 2EO 2EO Temperature 5050 50 50 50 70 70 70 70 70 PC Dose 0.16 0.16 0.16 0.16 0.16 0.16 0.160.16 0.16 0.16 Def none none TBP none TBP none none TBP none TBP Slump(in) 6.25 6.25 6.00 5.75 6.50 6.00 6.25 6.50 6.50 6.25 % Air 4.3 4.3 2.33.6 2.1 3.7 3.7 2.3 3.6 2.4 (Volumetric) PC = polycarboxylate dispersantASA = amine solubilizing agent Def = Defoamer

TABLE 5 Sample S90 S91 S92 S93 S94 S95 ASA None Oleyl Oleyl None DodecylDodecyl Amine Amine Dimethyl Dimethyl 2EO 2EO Amine Amine Temperature 5050 50 70 70 70 PC Dose 0.16 0.16 0.16 0.16 0.16 0.16 Def none none TBPnone none TBP AE-agent 0.6 0.6 0.6 0.6 0.6 0.6 (fl.oz/cwt) Slump (in)7.50 7.25 6.50 6.75 6.00 7.50 % Air 11.0 10.5 4.3 14.0 7.5 4.0(Volumetric) PC = polycarboxylate dispersant ASA = amine solubilizingagent Def = defoamer AE-agent = air entraining agent

TABLE 6 Sample S96 S97 S98 ASA None None Dodecyl Dimethyl Amine PC Dose0.08 0.08 0.08 Def none TBP TBP AE-agent (fl.oz/cwt) 0.3 0.3 0.3 Slump(in) 7.25 7.75 7.50 % Air (Volumetric) 8.5 7.0 5.0 PC = polycarboxylatedispersant ASA = amine solubilizing agent AE-agent = air entrainingagent Def = defoamer

The results shown in Tables 4, 5, and 6 demonstrate that the combinationof amine solubilizing agent and defoamer lowers concrete air contents atroom temperature (70° F.) and at colder temperatures (50° F.). As shownin Table 4 the air content of non-air-entrained concrete is reduced to adesirable level of less than 2.5%. In addition, the combination of aminesolubilizing agent and defoamer lowered concrete air contents in thepresence of an air-entraining agent at multiple levels ofpolycarboxylate dispersant as shown in Tables 5 and 6.

In Table 4 all the samples containing amine solubilizing agents (OleylAmine 2EO, Decyl Amine 2EO, Tallow Amine 2EO) and insoluble defoamer hadlower air contents than the samples with amine solubilizing agent alone.There was little or no difference between the air content of the control(no amine solubilizing agent or insoluble defoamer) and the sampleswithout the insoluble defoamer. This demonstrates that the defoamingpotential is governed primarily by the interaction of the insolubledefoamer and the amine solubilizing agent, rather than by the aminesolubilizing agent alone.

Table 5 demonstrates that with constant levels of air entrainer andpolycarboxylate dispersant the samples with the amine solubilizing agentand insoluble defoamer reduced the air content of the concrete mixtureby about one-half as compared to the control (no amine solubilizingagent or insoluble defoamer) and the samples without insoluble defoamer.

Table 6 shows that the greater defoaming performance from the aminesolubilizing agent and defoamer combination becomes even moreadvantageous at low dispersant dosages where air-entraining agentdosages can become so small that they are difficult to deliver reliablyunder field conditions.

Test solutions that were used to generate the data in Tables 7 and 8comprised water, an insoluble defoamer, amine solubilizing agent, andacetic acid. The amounts of the material shown are based on percent byweight of cement. The solutions were prepared by combining water, acid,amine solubilizing agent, and insoluble defoamer, then stirring with amagnetic stir bar in a glass beaker. The polycarboxylate dispersant wasadded as a separate solution to the cementitious mixture.

Table 7 summarizes performance data for an amine solubilizing agent,insoluble defoamer, and polycarboxylate dispersant in non-air-entrainedconcrete. All but one sample delivered 0.0032% TBP (tributylphosphate)and 0.0048% amine solubilizing agent by weight of cement for an aminesolubilizing agent to insoluble defoamer ratio of 1.5:1 unless otherwisestated. Slump and air content determinations were made after 5 minutesof mixing.

TABLE 7 % Air Aq. Def. PC Slump (volu- Soln Sample ASA Dose (in.)metric) Appearance S99 Oleyl Amine 2EO 0.08 8.00 2.5 Clear S100 StearylAmine 2EO 0.08 8.00 2.6 Cloudy S101 Tallow Amine 2EO 0.08 7.50 2.6 ClearS102 Tallow Amine 2PO 0.08 8.00 2.0 Clear S103 Tallow Amine 5EO 0.087.50 3.0 Cloudy S104 Tallow Amine 15EO 0.08 7.75 3.0 Cloudy S105 TallowAmine 15EO 0.08 7.75 5.7 Clear (2.5:1 ratio) S106 Oleamidopropyl 0.088.00 2.1 Clear dimethylamine S107 Stearamidopropyl 0.08 8.00 1.7 Cleardimethylamine S108 Lauramidopropyl 0.08 8.25 3.3 Clear dimethylamineS109 1-hydroxyethyl-2- 0.08 7.25 3.0 Clear oleylimidazoline S1101-hydroxyethyl-2- 0.08 7.25 3.5 Clear cocoimidazoline S111 None 0.088.25 2.0 Cloudy PC = polycarboxylate dispersant Def = defoamer ASA =amine solubilizing agent

The results in Table 7 demonstrate that the combination ofpolycarboxylate dispersant, amine solubilizing agent and defoamergenerally gave low air content in non-air-entrained concrete. The aminesolubilizing agents that contained shorter alkyl groups and higher EOcontent (Lauramidopropyl dimethylamine,1-hydroxyethyl-2-cocoimidazoline, Tallow Amine 5EOand Tallow Amine 15EO)had higher air contents than the corresponding lower EO or longer alkylchain containing amine solubilizing agents.

Table 8 summarizes performance data for an amine solubilizing agent,insoluble defoamer, and acetic acid solutions, and a separately addedpolycarboxylate dispersant in air entrained concrete. One sample (asnoted) was prepared as a clear solution of amine solubilizing agent,insoluble defoamer, acetic acid, and polycarboxylate dispersant. Two airentraining agents, both commercially available, proprietary products,AE®90 admixture, manufactured by Master Builders, Inc., Cleveland, Ohio,and Micro-Air admixture, were used at the dosages indicated in Table 8.All samples delivered 0.0032% TBP (Tributyl Phosphate) and 0.0048% aminesolubilizing agent by weight of cement unless otherwise stated.

TABLE 8 Aq. Def. PC AEA Slump % Soln Sample ASA Dose AEA Dose (in.) AirAppearance S112 Oleyl Amine 2EO 0.08 Micro- 0.25 8.00 6.1 Clear Air S113Oleyl Amine 2EO + PC 0.08 Micro- 0.25 8.00 0.5 Clear with Air PC S114Tallow Amine 2EO 0.08 Micro- 0.25 7.75 6.0 Clear Air S115 Tallow Amine2PO 0.08 Micro- 0.25 8.00 6.5 Clear Air S116 Tallow Amine 5EO 0.08Micro- 0.25 8.00 11.0 Clear (2.5:1 ratio) Air S117 Oleamidopropyl 0.08Micro- 0.25 8.00 10.5 Clear dimethylamine Air S118 1-hydroxyethyl-2-0.08 Micro- 0.25 8.50 12.0 Clear Oleylimidazoline Air S119 Oleyl Amine2EO 0.08 AE90 1.2 8.00 5.5 Clear S120 Tallow Amine 2EO 0.08 AE90 1.27.75 6.0 Clear S121 Tallow Amine 5EO 0.08 AE90 1.2 7.75 5.8 Clear S122Tallow Amine 2PO 0.08 AE90 1.2 7.75 6.0 Clear S123 Oleamidopropyl 0.08AE90 1.2 7.75 11.0 Clear dimethylamine S124 Oleamidopropyl 0.08 AE90 0.67.75 7.5 Clear dimethylamine PC = polycarboxylate dispersant Def =defoamer ASA = amine solubilizing agent AEA = Air-entraining agent

These results demonstrate that the combination of amine solubilizingagent and defoamer can be used with different air-entraining agentchemistries to entrain desired and controlled air contents in concrete.Lower air contents were generally obtained with lower alkoxylate aminesolubilizing agent's compared with other amine solubilizing agents.Additionally, the air content of the Oleamidopropyl dimethylamine samplewas reduced to an acceptable level when the dosage of AE90 air entrainerwas reduced.

Therefore, the present invention provides an admixture containing awater insoluble defoamer, an amine solubilizing agent capable ofsolubilizing the water insoluble defoamer in an acidic medium, andoptionally a dispersant for cementitious compositions, for controllingthe amount of air in a predictable manner in cementitious compositions.

The present invention also provides a cementitious compositioncomprising cementitious material, water, a water insoluble defoamer, anamine solubilizing agent capable of solubilizing the water insolubledefoamer, and optionally a dispersant for cementitious compositions, forcontrolling the amount of air in a predictable manner in thecementitious composition.

The present invention also provides a method of making a cementitiouscomposition comprising mixing cementitious material, water, a waterinsoluble defoamer, an amine solubilizing agent capable of solubilizingthe water insoluble defoamer, and optionally a dispersant forcementitious compositions, for controlling the amount of air in apredictable manner in the cementitious composition.

It should be appreciated that the present invention is not limited tothe specific embodiments described above, but includes variations,modifications and equivalent embodiments defined by the followingclaims. The embodiments disclosed alone are not necessarily in thealternative, as various embodiments of the invention may be combined toprovide desired characteristics or results.

1. An admixture composition for cementitious compositions comprising awater insoluble defoamer, an amine solubilizing agent capable ofsolubilizing the water insoluble defoamer in an acidic medium that is atleast one of a (mono, di, tri or tetra)alkyl ether amine, alkoxylatedamine, alkyl amide amine, alkyl imidazoline, alkyl (di, tri or tetra)ether amine, alkoxylated (di or tri)amine, ethoxylated alkyl etheramine, or mixtures thereof, and optionally a dispersant for cementitiouscompositions.
 2. A cementitious composition comprising cementitiousmaterial, a water insoluble defoamer, an amine solubilizing agentcapable of solubilizing the water insoluble defoamer that is at leastone of a (mono, di, tri or tetra)alkyl ether amine, alkoxylated amine,alkyl amide amine, alkyl imidazoline, alkyl (di, tri or tetra) etheramine, alkoxylated (di or tri)amine, ethoxylated alkyl ether amine, ormixtures thereof, and optionally a dispersant for cementitiouscompositions.
 3. The composition of claim 1 or 2 further characterizedin that prior to addition to cementitious material the acidic medium isfirst combined with the amine solubilizing agent capable of solubilizingthe water insoluble defoamer, followed by the water insoluble defoamer,then optionally the dispersant.
 4. The composition of claim 1 or 2further characterized, in that prior to addition to cementitiousmaterial the water insoluble defoamer, the amine solubilizing agentcapable of solubilizing the water insoluble defoamer, and optionally thedispersant for cementitious compositions are combined with an acidicmedium in combination.
 5. The composition of claim 1 or 2 wherein theamine solubilizing agent comprises a total of about 8 carbons to abour100 carbons.
 6. The composition of claim 1 or 2 wherein the aminesolubilizing agent comprises less than about 30 ethoxylate units.
 7. Thecomposition of claim 1 or 2 wherein the amine solubilizing agentcomprises less than about 15 ethoxylate units.
 8. The composition ofclaim 1 or 2, wherein the (mono, di, tri or tetra)alkyl ether amine isat least one of decyl ether amine or tetradecyl ether amine, or mixturesthereof.
 9. The composition of claim 1 or 2, wherein the alkoxylatedamine is at least one of an ethoxylated(2)cocoalkyl amine,propoxylated(2)tallowalkyl amine, bis (2-hydroxyethyl)oleyl amine, bis(2-hydroxyethyl)octadecyl amine, polyoxyethylene(3-15)tallowalkyl amine,bis (2-hydroxyethyl)cocoalkyl amine N-oleyl-1,1-iminobis-2-propanol, ormixtures thereof.
 10. The composition of claim 1 or 2, wherein the alkylamide amine is at least one of a lauramidopropyl dimethylamine,stearamidopropyl dimethylamine, oleamidopropyl dimethylamine, ormixtures thereof.
 11. The composition of claim 1 or 2, wherein the alkylimidazoline is at least one of1-(2-hydroxyethyl)-2-(heptadecenyl)imidazoline, oleyl hydroxyethylimidazoline, cocoalkyl hydroxyethyl imididazoline, or mixtures thereof.12. The composition of claim 1 or 2, wherein the alkyl (di, tri ortetra) ether amine is at least one of isotridecyloxypropyl-1,3-diaminopropane, tetradecyloxypropyl-1,3-diaminopropane or mixtures thereof.
 13. Thecomposition of claim 1 or 2, wherein the alkoxylated (di or tri) amineis ethoxylated (3)N-tallow-1,3-diaminopropane.
 14. The composition ofclaim 1 or 2, wherein the amine solubilizing agent is activated with anacid.
 15. The composition of claim 14, wherein the amine solubilizingagent is deactivated at an alkaline pH.
 16. The composition of claim 1or 2 further comprising an air entraining agent.
 17. The composition ofclaim 1 or 2 further comprising at least one of set accelerators, setretarders, air detraining agents, foaming agents, dampproofingadmixtures, pumping aids, fungicidal admixtures, insecticidaladmixtures, germicidal admixtures, alkali activity reducers, bondingadmixtures, corrosion inhibitors, or pigments.
 18. The composition ofclaim 1 or 2, wherein prior to addition to cementitious material theamine solubilizing agent is present in an amount sufficient to form astable micellar solution.
 19. The composition of claim 1, wherein thecomposition comprises about 0.02% to about 60% amine solubilizing agent,about 0.02% to about 30% insoluble defoamer, about 0 to about 60%dispersant for cementitious compositions, and 0 to about 25% of an acidbased on weight of dry solids.
 20. The composition of claim 19, whereinthe composition comprises about 0.25% to about 10% insoluble defoamerbased on weight of dry solids.
 21. The composition of claim 2 whereinthe amine solubilizing agent is present in an amount from about 0.0001%to about 0.2% primary active ingredient; the insoluble defoamer ispresent in an amount from about 0.0001% to about 0.1% primary activeingredient; the dispersant for cementitious compositions is present inan amount from 0 to about 2% primary active ingredient; and an acid ispresent in an amount from 0 to about 2% primary active ingredient basedon the dry weight of the cementitious material.
 22. The composition ofclaim 21 wherein the dispersant for cementitious compositions is presentin an amount from about 0.05% to about 0.5% primary active ingredientbased on the dry weight of the cementitious material.
 23. Thecomposition of claim 1 or 2, wherein the water insoluble defoamer is atleast one of a mineral oil, a vegetable oil, a fatty acid ester, anether compound, a hydroxyl functional compound, an alcohol, a phosphoricester, a silicone, polyoxyalkylene, a polymer comprising at least one ofpropylene oxide or ethylene oxide moieties, a hydrocarbon, or anacetylenic compound.
 24. The composition of claim 1 or 2, wherein thewater insoluble defoamer is at least one of nonyl phenol, polypropyleneoxide, triisobutyl phosphate, kerosene, liquid paraffin, animal oil,vegetable oil, sesame oil, castor oil, alkylene oxide, natural wax,linear or branched fatty alcohols and their alkoxylated derivatives,octyl alcohol, hexadecyl alcohol, acetylenic alcohol, acetylinic alcoholalkoxylates, glycols, polyoxyalkylene glycol, polyoxyalkylene amide,acrylate polyamine, tributyl phosphate, silicone oil, silicone paste,silicone emulsion, organic modified polysiloxane, fluorosilicone oil; orpolyoxyethylene polyoxypropylene adducts.
 25. The composition of claim2, wherein the cement is selected from the group consisting of portlandcement, masonry cement, alumina cement, refractory cement, magnesiacement, calcium sulfoaluminate cement, oil well cement, and mixturesthereof.
 26. The composition of claim 2 further comprising a cementadmixture or additive that is at least one of pozzolan, calcine clay, oraggregate.
 27. The cementitious composition of claim 26, wherein theaggregate is at least one of silica, quartz, crushed round marble, glassspheres, granite, limestone, calcite, feldspar, alluvial sands, or sand.28. The cementitious composition of claim 26, wherein the pozzolan is atleast one of natural pozzolan, fly ash, silica fume, calcined clay, orblast furnace slag.
 29. The composition of claim 1 or 2 wherein thedispersant for cementitious compositions is at least one polycarboxylatehigh range water reducing dispersant selected from the group consistingof: a) a dispersant of Formula (I):

wherein in Formula (I) X is at least one of hydrogen, an alkali earthmetal ion, an alkaline earth metal ion, ammonium ion, or amine; R is atleast one of C₁ to C₆ alkyl(ene) ether or mixtures thereof or C₁ to C₆alkyl(ene) imine or mixtures thereof; Q is at least one of oxygen, NH,or sulfur; p is a number from 1 to about 300 resulting in at least oneof a linear side chain or branched side chain; R₁ is at least one ofhydrogen, C₁ to C₂₀ hydrocarbon, or functionalized hydrocarboncontaining at least one of —OH, —COOH, an ester or amide derivative of—COOH, sulfonic acid, an ester or amide derivative of sulfonic acid,amine, or epoxy; Y is at least one of hydrogen, an alkali earth metalion, an alkaline earth metal ion, ammonium ion, amine, a hydrophobichydrocarbon or polyalkylene oxide moiety that functions as a defoamer;m, m′, m″, n, n′, and n″ are each independently 0 or an integer between1 and about 20; Z is a moiety containing at least one of i) at least oneamine and one acid group, ii) two functional groups capable ofincorporating into the backbone selected from the group consisting ofdianhydrides, dialdehydes, and di-acid-chlorides, or iii) an imideresidue; and wherein a, b, c, and d reflect the mole fraction of eachunit wherein the sum of a, b, c, and d equal one, wherein a, b, c, and dare each a value greater than or equal to zero and less than one, and atleast two of a, b, c and d are greater than zero; b) a dispersant ofFormula (II):

wherein in Formula (II): A is COOM or optionally in the “y” structure anacid anhydride group (—CO—O—CO—) is formed in place of the A groupsbetween the carbon atoms to which the A groups are bonded to form ananhydride; B is COOM M is hydrogen, a transition metal cation, theresidue of a hydrophobic polyalkylene glycol or polysiloxane, an alkalimetal ion, an alkaline earth metal ion, ferrous ion, aluminum ion,(alkanol)ammonium ion, or (alkyl)ammonium ion; R is a C₂₋₆ alkyleneradical; R1 is a C₁₋₂₀ alkyl, C₆₋₉ cycloalkyl, or phenyl group; x, y,and z are a number from 0.01 to 100; m is a number from 1 to 100; and nis a number from 10 to 100; c) a dispersant comprising at least onepolymer or a salt thereof having the form of a copolymer of i) a maleicanhydride half-ester with a compound of the formula RO(AO)_(m)H, whereinR is a C₁-C₂₀ alkyl group, A is a C₂₋₄ alkylene group, and m is aninteger from 2-16; and ii) a monomer having the formulaCH₂═CHCH₂—(OA)_(n)OR, wherein n is an integer from 1-90 and R is a C₁₋₂₀alkyl group; d) a dispersant obtained by copolymerizing 5 to 98% byweight of an (alkoxy)polyalkylene glycol mono(meth)acrylic ester monomer(a) represented by the following general formula (1):

wherein R₁ stands for hydrogen atom or a methyl group, R₂O for onespecies or a mixture of two or more species of oxyalkylene group of 2 to4 carbon atoms, providing two or more species of the mixture may beadded either in the form of a block or in a random form, R₃ for ahydrogen atom or an alkyl group of 1 to 5 carbon atoms, and m is a valueindicating the average addition mol number of oxyalkylene groups that isan integer in the range of 1 to 100, 95 to 2% by weight of a(meth)acrylic acid monomer (b) represented by the above general formula(2), wherein R₄ and R₅ are each independently hydrogen atom or a methylgroup, and M₁ for a hydrogen atom, a monovalent metal atom, a divalentmetal atom, an ammonium group, or an organic amine group, and 0 to 50%by weight of other monomer (c) copolymerizable with these monomers,provided that the total amount of (a), (b), and (c) is 100% by weight;e) a graft polymer that is a polycarboxylic acid or a salt thereof,having side chains derived from at least one species selected from thegroup consisting of oligoalkyleneglycols, polyalcohols, polyoxyalkyleneamines, and polyalkylene glycols; f) a reaction product of component A,optionally component B, and component C; wherein each component A isindependently a nonpolymeric, multi-functional moiety or combination ofmono or multifunctional moieties that adsorbs onto a cementitiousparticle, and contains at least one residue derived from a firstcomponent select from the group consisting of phosphates, phosphonates,phosphinates, hypophosphites, sulfates, sulfonates, sulfinates, alkyltrialkoxy silanes, alkyl triacyloxy silanes, alkyl triaryloxy silane,borates, boronates, boroxines, phosphoraniides, amines, amides,quaternary ammonium groups, carboxylic acids, carboxylic acid ester,alcohols, carbohydrates, phosphate esters of sugars, borate esters ofsugars, sulfate esters of sugars, salts of any of the precedingmoieties, and mixtures thereof; wherein component B is an optionalmoiety, where if present, each component B is independently anonpolymeric moiety that is disposed between the component A moiety andthe component C moiety, and is derived from a second component selectfrom the group consisting of linear saturated hydrocarbons, linearunsaturated hydrocarbons, saturated branched hydrocarbons, unsaturatedbranched hydrocarbons, alicyclic hydrocarbons, heterocyclichydrocarbons, aryl, phosphoester, nitrogen containing compounds, andmixtures thereof; and wherein component C is at least one moiety that islinear or branched water soluble, nonionic polymer substantiallynon-adsorbing to cement particles, and is selected from the groupconsisting of poly(oxyallcylene glycol), poly(oxyalkylene amine),poly(oxyalkylene diamine), monoalkoxy poly(oxyalkylene amine),monoaryloxy poly(oxyalkylene amine), monoalkoxy poly(oxyalkylen glycol),monoaryloxy poly(oxyalkylene glycol), poly(vinyl pyrrolidones),poly(methyl vinyl ethers), poly(ethylene imines), poly(acrylamides),polyoxazoles, and mixtures thereof; and g) a dispersant of Formula(III):

wherein in Formula (III): D=a component selected from the groupconsisting of the structure d1, the structure d2, and mixtures thereof;X=H, CH₃, C₂ to C₆ Alkyl, Phenyl, p-Methyl Phenyl, or Sulfonated Phenyl;Y=H or —COOM; R=H or CH₃; Z=H, —SO₃M, —PO₃M, —COOM, —O(CH₂)_(n)OR₃ wheren=2 to 6, —COOR₃, or —(CH₂)_(n)OR₃ where n=0 to 6, —CONHR₃,—CONHC(CH₃)₂CH₂SO₃M, —COO(CHR₄)_(n)OH where n=2 to 6, or —O(CH₂)_(n)OR₄wherein n=2 to 6; R₁, R₂, R₃, R₅ are each independently —(CHRCH₂O)_(m)R₄random copolymer of oxyethylene units and oxypropylene units where m=10to 500 and wherein the amount of oxyethylene in the random copolymer isfrom about 60% to 100% and the amount of oxypropylene in the randomcopolymer is from 0% to about 40%; R₄=H, Methyl, C₂ to about C₆ Alkyl,or about C₆ to about C₁₀ aryl; M=H, Alkali Metal, Alkaline Earth Metal,Ammonium, Amine, triethanol amine, Methyl, or C₂ to about C₆ Alkyl; a=0to about 0.8; b=about 0.2 to about 1.0; c=0 to about 0.5; d=0 to about0.5; and wherein a, b, c, and d represent the mole fraction of each unitand the sum of a, b, c, and d is 1.0; h) a dispersant of Formula (IV):

wherein in Formula (IV): the “b” structure is one of a carboxylic acidmonomer, an ethylenically unsaturated monomer, or maleic anhydridewherein an acid anhydride group (—CO—O—CO—) is formed in place of thegroups Y and Z between the carbon atoms to which the groups Y and Z arebonded respectively, and the “b” structure must include at least onemoiety with a pendant ester linkage and at least one moiety with apendant amide linkage; X=H, CH₃, C₂ to C₆ Alkyl, Phenyl, p-MethylPhenyl, p-Ethyl Phenyl, Carboxylated Phenyl, or Sulfonated Phenyl; Y=H,—COOM, —COOH, or W; W=a hydrophobic defoamer represented by the formulaR₅O—(CH₂CH₂O)_(s)—(CH₂C(CH₃)HO)_(t)—(CH₂CH₂O)_(u) where s, t, and u areintegers from 0 to 200 with the proviso that t>(s+u) and wherein thetotal amount of hydrophobic defoamer is present in an amount less than10% by weight of the polycarboxylate dispersant; Z=H, —COOM,—O(CH₂)_(n)OR₃ where n=2 to 6, —COOR₃, —(CH₂)_(n)OR₃ where n=0 to 6, or—CONHR₃; R₁=H, or CH₃; R₂, R₃, are each independently a random copolymerof oxyethylene units and oxypropylene units of the general formula—(CH(R₁)CH₂O)_(m)R₄ where m=10 to 500 and wherein the amount ofoxyethylene in the random copolymer is from about 60% to 100% and theamount of oxypropylene in the random copolymer is from 0% to about 40%;R₄=H, Methyl, or C₂ to C₈ Alkyl; R₅=C₁ to C₁₈ alkyl or C₆ to C₁₈ alkylaryl; M=Alkali Metal, Alkaline Earth Metal, Ammonia, Amine, monoethanolamine, diethanol amine, triethanol amine, morpholine, imidazole;a=0.01-0.8; b=0.2-0.99; c=0-0.5; and wherein a, b, c represent the molefraction of each unit and the sum of a, b, and c, is 1; i) a randomcopolymer corresponding to the following Formula (V) in free acid orsalt form having the following monomer units and numbers of monomerunits:

wherein A is selected from the moieties (i) or (ii)

wherein R₁ and R₃ are selected from the group consisting of substitutedbenzene, C₁₋₈ alkyl, C₂₋₈ alkenyl, C₂₋₈ alkylcarbonyl, C₁₋₈ alkoxy,carboxyl, hydrogen, and a ring, R₂ and R₄ are selected from the groupconsisting of hydrogen and C₁₋₄ alkyl, wherein R₁ and R₃ can togetherwith R₂ and/or R₄ when R₂ and/or R₄ are C₁₋₄ alkyl form the ring; R₇,R₈, R₉, and R₁₀ are individually selected from the group consisting ofhydrogen, C₁₋₆ alkyl, and a C₂₋₈ hydrocarbon chain, wherein R₁ and R₃together with R₇ and/or R₈, R₉, and R₁₀ form the C₂₋₈ hydrocarbon chainjoining the carbon atoms to which they are attached, the hydrocarbonchain optionally having at least one anionic group, wherein the at leastone anionic group is optionally sulfonic; M is selected from the groupconsisting of hydrogen, and the residue of a hydrophobic polyalkyleneglycol or a polysiloxane, with the proviso that when A is (ii) and M isthe residue of a hydrophobic polyalkylene glycol, M must be differentfrom the group —(R₅O)_(m)R₆; R₅ is a C₂₋₈ alkylene radical; R₆ isselected from the group consisting of C₁₋₂₀ alkyl, C₆₋₉ cycloalkyl andphenyl; n, x, and z are numbers from 1 to 100; y is 0 to 100; m is 2 to1000; the ratio of x to (y+z) is from 1:10 to 10:1 and the ratio of y:zis from 5:1 to 1:100; j) a copolymer of oxyalkyleneglycol-alkenyl ethersand unsaturated dicarboxylic acids, comprising: i) 0 to 90 mol % of atleast one component of the formula 3a or 3b:

wherein M is a hydrogen atom, a mono- or divalent metal cation, anammonium ion or an organic amine residue, a is 1, or when M is adivalent metal cation a is ½; wherein X is —OM_(a),—O—(C_(m)H_(2m)O)_(n)—R¹ in which R¹ is a hydrogen atom, an aliphatichydrocarbon radical containing from 1 to 20 carbon atoms, acycloaliphatic hydrocarbon radical containing 5 to 8 carbon atoms or anoptionally hydroxyl, carboxyl, C₁₋₁₄ alkyl, or sulphonic substitutedaryl radical containing 6 to 14 carbon atoms m is 2 to 4, and n is 0 to100, —NHR₂, —N(R²)₂ or mixtures thereof in which R²=R¹ or —CO—NH₂; andwherein Y is an oxygen atom or —NR²; ii) 1 to 89 mol % of components ofthe general formula 4:

wherein R₃ is a hydrogen atom or an aliphatic hydrocarbon radicalcontaining from 1 to 5 carbon atoms, p is 0 to 3, and R₁ is hydrogen, analiphatic hydrocarbon radical containing from 1 to 20 carbon atoms, acycloaliphatic hydrocarbon radical containing 5 to 8 carbon atoms or anoptionally hydroxyl, carboxyl, C₁₋₁₄ alkyl, or sulfonic substituted arylradical containing 6 to 14 carbon atoms, is 2 to 4, and n is 0 to 100,and iii) 0.1 to 10 mol % of at least one component of the formula 5a or5b:

wherein S is a hydrogen atom or —COOM_(a) or —COOR₅, T is —COOR₅, —W—R₇,—CO—[—NH—(CH2)3)-]_(s)—W—R₇, —CO—O—(CH₂)_(z)—W—R₇, a radical of thegeneral formula:

or —(CH₂)_(z)—V—(CH₂)_(z)—CH═CH—R₁, or when S is —COOR₅ or —COOM_(a), U₁is —CO—NHM—, —O— or —CH₂O, U₂ is —NH—CO—, —O— or —OCH₂, V is—O—CO—C₆H₄—CO—O— or —W—, and W is

R4 is a hydrogen atom or a methyl radical, R5 is aliphatic hydrocarbonradical containing 3 to 20 carbon atoms, a cycloaliphatic hydrocarbonradical containing 5 to 8 carbon atoms or an aryl radical containing 6to 14 carbon atoms, R₆=R₁ or

R₇=R₁ or

r is 2 to 100, s is 1 or 2, x is 1 to 150, y is 0 to 15 and z is 0 to 4;iv) 0 to 90 mol % of at least one component of the formula 6a, 6b, or6c:

wherein M is a hydrogen atom, a mono- or divalent metal cation, anammonium ion or an organic amine residue, a is 1, or when M is adivalent metal cation a is ½; wherein X is —OM_(a),—O—(C_(m)H_(2m)O)_(n)—R¹ in which R¹ is a hydrogen atom, an aliphatichydrocarbon radical containing from 1 to 20 carbon atoms, acycloaliphatic hydrocarbon radical containing 5 to 8 carbon atoms or anoptionally hydroxyl, carboxyl, C₁₋₁₄ alkyl, or sulphonic substitutedaryl radical containing 6 to 14 carbon atoms m is 2 to 4, and n is 0 to100, —NH—(C _(m)H_(2m)O)_(n)—R¹, —NH₂, —N(R²)₂ or mixtures thereof inwhich R²=R¹ or —CO—NH₂; and wherein Y is an oxygen atom or —NR²; k) acopolymer of dicarboxylic acid derivatives and oxyalkyleneglycol-alkenyl ethers, comprising: i) 1 to 90 mol. % of at least onemember selected from the group consisting of structural units of Formula7a and Formula 7b:

wherein M is H, a monovalent metal cation, a divalent metal cation, anammonium ion or an organic amine; a is ½ when M is a divalent metalcation or 1 when M is a monovalent metal cation; wherein R¹ is —OM_(a),or —O—(C_(m)H_(2m)O)_(n)—R² wherein R² is H, a C₁₋₂₀ aliphatichydrocarbon, a C₅₋₈ cycloaliphatic hydrocarbon, or a C₆₋₁₄ aryl that isoptionally substituted with least one member selected from the groupconsisting of [—COOM_(a), —(SO₃)M_(a), and —(PO₃)M_(a2)]; m is 2 to 4; nis 1 to 200; ii) 0.5 to 80 mol. % of the structural units of Formula 8:

wherein R³ is H or a C₁₋₅ aliphatic hydrocarbon; p is 0 to 3; R² is H, aC₁₋₂₀ aliphatic hydrocarbon, a C₅₋₈ cycloaliphatic hydrocarbon, or aC₆₋₁₄ aryl that is optionally substituted with at least one memberselected from the group consisting of [—COOM_(a), —(SO₃)M_(a), and—(PO₃)M_(a2)]; m is 2 to 4; n is 1 to 200; iii) 0.5 to 80 mol. %structural units selected from the group consisting of Formula 9a andFormula 9b:

wherein R⁴ is H, C₁₋₂₀ aliphatic hydrocarbon that is optionallysubstituted with at least one hydroxyl group, —(C_(m)H_(2m)O)_(n)—R²,—CO—NH—R², C₅₋₈ cycloaliphatic hydrocarbon, or a C₆₋₁₄ aryl that isoptionally substituted with at least one member selected from the groupconsisting of [—COOM_(a), —(SO₃)M_(a), and —(PO₃)M_(a2)]; M is H, amonovalent metal cation, a divalent metal cation, an ammonium ion or anorganic amine; a is ½ when M is a divalent metal cation or 1 when M is amonovalent metal cation; R² is H, a C₁₋₂₀ aliphatic hydrocarbon, a C₅₋₈cycloaliphatic hydrocarbon, or a C₆₋₁₄ aryl that is optionallysubstituted with at least one member selected from the group consistingof [—COOM_(a), —(SO₃)M_(a), and —(PO₃)M_(a2)]; m is 2 to 4; n is 1 to200; iv) 1 to 90 mol. % of structural units of Formula 10

wherein R⁵ is methyl, or methylene group, wherein R⁵ forms one or more 5to 8 membered rings with R⁷; R⁶ is H, methyl, or ethyl; R⁷ is H, a C₁₋₂₀aliphatic hydrocarbon, a C₆₋₁₄ aryl that is optionally substituted withat least one member selected from the group consisting of [—COOM_(a),—(SO₃)M_(a), and —(PO₃)M_(a2)], a C₅₋₈ cycloaliphatic hydrocarbon,—OCOR⁴, —OR⁴, or —COOR⁴, wherein R⁴ is H, a C₁₋₂₀ aliphatic hydrocarbonthat is optionally substituted with at least one —OH,—(C_(m)H_(2m)O)_(n)—R², —CO—NH—R², C₅₋₈ cycloaliphatic hydrocarbon, or aC₆₋₁₄ aryl residue that is optionally substituted with a member selectedfrom the group consisting of [—COOM_(a), —(SO₃)M_(a), —(PO₃)M_(a2)]. 30.A method of making a cementitious composition comprising mixing thecomposition of claim 29 containing cementitious material with water. 31.The method of claim 30, wherein the amine solubilizing agent isactivated with an acid.
 32. The method of claim 31, includingdeactivating the amine solubilizing agent at an alkaline pH.
 33. Themethod of claim 30 wherein the amine solubilizing agent comprises atotal of about 8 carbons to about 100 carbons.
 34. The method of claim30 wherein the amine solubilizing agent comprises less than about 30ethoxylate units.
 35. The method of claim 30 wherein the aminesolubilizing agent comprises less than about 15 ethoxylate units. 36.The method of claim 30 wherein the amine solubilizing agent is presentin an amount from about 0.0001% to about 0.2% primary active ingredient;the insoluble defoamer is present in an amount from about 0.0001% toabout 0.1% primary active ingredient; the dispersant for cementitiouscompositions is present in an amount from 0 to about 2% primary activeingredient; and an acid is present in an amount from 0 to about 2%primary active ingredient based on the dry weight of the cementitiousmaterial.
 37. The method of claim 36 wherein the dispersant forcementitious compositions is present in an amount from about 0.05% toabout 0.5% primary active ingredient based on the dry weight of thecementitious material.
 38. The method of claim 30 further characterizedin that prior to addition to cementitious material the acidic medium isfirst combined with the amine solubilizing agent capable of solubilizingthe water insoluble defoamer, followed by the water insoluble defoamer,then optionally the dispersant.
 39. The method of claim 30 furthercharacterized, in that prior to addition to cementitious material thewater insoluble defoamer, the amine solubilizing agent capable ofsolubilizing the water insoluble defoamer, and optionally the dispersantfor cementitious compositions are combined with an acidic medium incombination.
 40. The method of claim 30, wherein the (mono, di, tri ortetra)alkyl ether amine is at least one of decyl ether amine, tetradecylether amine, or mixtures thereof.
 41. The method of claim 30, whereinthe alkoxylated amine is at least one of an ethoxylated(2)cocoalkylamine, propoxylated(2)tallowalkyl amine, bis (2-hydroxyethyl)oleylamine, bis (2-hydroxyethyl)octadecyl amine,polyoxyethylene(3-15)tallowalkyl amine, bis (2-hydroxyethyl)cocoalkylamine or N-oleyl-1,1-iminobis-2-propanol, or mixtures thereof.
 42. Themethod of claim 30, wherein the alkyl amide amine is at least one of alauramidopropyl dimethylamine, stearamidopropyl dimethylamine,oleamidopropyl dimethylamine, or mixtures thereof.
 43. The method ofclaim 30, wherein the alkyl imidazoline is at least one of1-(2-hydroxyethyl)-2-(heptadecenyl)imidazoline, oleyl hydroxyethylimidazoline, cocoalkyl hydroxyethyl imididazoline, mixtures thereof. 44.The method of claim 30, wherein the alkyl (di, tri or tetra) ether amineis at least one of iso tridecyloxypropyl-1,3-diaminopropane, tetradecyloxypropyl-1,3-diaminopropane or mixtures thereof.
 45. The method ofclaim 30, wherein the alkoxylated (di or tri) amine is ethoxylated(3)N-tallow-1,3-diaminopropane.
 46. The method of claim 30, wherein thewater insoluble defoamer is at least one of a mineral oil, a vegetableoil, a fatty acid ester, an ether compound, a hydroxyl functionalcompound, an alcohol, a phosphoric ester, a silicone, polyoxyalkylene, apolymer comprising at least one of propylene oxide or ethylene oxidemoieties, a hydrocarbon, or an acetylenic compound.
 47. The method ofclaim 30, wherein the water insoluble defoamer is at least one of nonylphenol, polypropylene oxide, triisobutyl phosphate, kerosene, liquidparaffin, animal oil, vegetable oil, sesame oil, castor oil, alkyleneoxide , natural wax, linear or branched fatty alcohols and theiralkoxylated derivatives, octyl alcohol, hexadecyl alcohol, acetylenealcohol, acetylinic alcohol alkoxylates, glycols, polyoxyalkyleneglycol, polyoxyalkylene amide, acrylate polyamine, tributyl phosphate,silicone oil, silicone paste, silicone emulsion, organic modifiedpolysiloxane, fluorosilicone oil; or polyoxyethylene polyoxypropyleneadducts.
 48. The method of claim 30, wherein the cement is selected fromthe group consisting of portland cement, masonry cement, alumina cement,refractory cement, magnesia cement, calcium sulfoaluminate cement, oilwell cement, and mixtures thereof.
 49. The method of claim 30 furthercomprising mixing a cement admixture or additive into the cementitiouscomposition, wherein the cement admixture or additive is at least one ofset accelerators, set retarders, air detraining agents, foaming agents,dampproofing admixture, pumping aids, fungicidal admixtures,insecticidal admixtures, germicidal admixtures, alkali activityreducers, bonding admixtures, corrosion inhibitors, pozzolans, clay,pigments, or aggregates.
 50. The method of claim 49 wherein theaggregate is at least one of silica, quartz, crushed round marble, glassspheres, granite, limestone, calcite, feldspar, alluvial sands, or sand.51. The method of claim 49, wherein the pozzolan is at least one ofnatural pozzolan, fly ash, silica fume, calcined clay, or blast furnaceslag.
 52. The method of claim 30, wherein prior to addition tocementitious material the amine solubilizing agent is present in anamount sufficient to form a stable micellar solution.
 53. The method ofclaim 30, wherein the water insoluble defoamer, the amine solubilizingagent capable of solubilizing the water insoluble defoamer, andoptionally the dispersant for cementitious compositions are added as onesolution to cementitious material.
 54. A method of making a cementitiouscomposition comprising mixing cementitious material, water, a waterinsoluble defoamer, an amine solubilizing agent capable of solubilizingthe water insoluble defoamer that is at least one of a (mono, di, tri ortetra)alkyl ether amine, alkoxylated amine, alkyl amide amine, alkylimidazoline, alkyl (di, tri or tetra) ether amine, alkoxylated (di ortri)amine, ethoxylated alkyl ether amine, or mixtures thereof, andoptionally a dispersant for cementitious compositions.
 55. The method ofclaim 54, wherein the amine solubilizing agent is activated with anacid.
 56. The method of claim 55, wherein the amine solubilizing agentis deactivated at an alkaline pH.
 57. The method of claim 54 wherein theamine solubilizing agent comprises a total of about 8 carbons to about100 carbons.
 58. The method of claim 54 wherein the amine solubilizingagent comprises less than about 30 ethoxylate units.
 59. The method ofclaim 54 wherein the amine solubilizing agent comprises less than about15 ethoxylate units.
 60. The method of claim 54 wherein the aminesolubilizing agent is present in an amount from about 0.001% to about0.2% primary active ingredient; the insoluble defoamer is present in anamount from about 0.0001% to about 0.1% primary active ingredient; thedispersant for cementitious compositions is present in an amount from 0to about 2% primary active ingredient; and an acid is present in anamount from 0 to about 2% primary active ingredient based on the dryweight of the cementitious material.
 61. The method of claim 60 whereinthe dispersant for cementitious compositions is present in an amountfrom about 0.05% to about 0.5% primary active ingredient based on thedry weight of the cementitious material.
 62. The method of claim 54further characterized in that prior to addition to cementitious materialan acidic medium is first combined with the amine solubilizing agentcapable of solubilizing the water insoluble defoamer, followed by thewater insoluble defoamer, then optionally the dispersant.
 63. The methodof claim 54 further characterized, in that prior to addition tocementitious material the water insoluble defoamer, the aminesolubilizing agent capable of solubilizing the water insoluble defoamer,and optionally the dispersant for cementitious compositions are combinedwith an acidic medium in combination.
 64. The method of claim 54,wherein the (mono, di, tri or tetra)alkyl ether amine is at least one ofdecyl ether amine, tetradecyl ether amine, or mixtures thereof.
 65. Themethod of claim 54, wherein the alkoxylated amine is at least one of anethoxylated(2)cocoalkyl amine, propoxylated(2)tallowalkyl amine, bis(2-hydroxyethyl)oleyl amine, bis (2-hydroxyethyl)octadecyl amine,polyoxyethylene(3-15)tallowalkyl amine, bis (2-hydroxyethyl)cocoalkylamine or N-oleyl-1,1-iminobis-2-propanol, or mixtures thereof.
 66. Themethod of claim 54, wherein the alkyl amide amine is at least one of alauramidopropyl dimethylamine, stearamidopropyl dimethylamine,oleamidopropyl dimethylamine, or mixtures thereof.
 67. The method ofclaim 54, wherein the alkyl imidazoline is at least one of1-(2-hydroxyethyl)-2-(heptadecenyl)imidazoline, oleyl hydroxyethylimidazoline, cocoalkyl hydroxyethyl imididazoline, or mixtures thereof.68. The method of claim 54, wherein the alkyl (di, tri or tetra) etheramine is at least one of iso tridecyloxypropyl-1,3-diaminopropane, tetradecyloxypropyl-1,3-diaminopropane or mixtures thereof.
 69. The method ofclaim 54, wherein the alkoxylated (di or tri) amine is ethoxylated(3)N-tallow-1,3-diaminopropane.
 70. The method of claim 54, wherein thewater insoluble defoamer is at least one of a mineral oil, a vegetableoil, a fatty acid ester, an ether compound, a hydroxyl functionalcompound, an alcohol, a phosphoric ester, a silicone, polyoxyalkylene, apolymer comprising at least one of propylene oxide or ethylene oxidemoieties, a hydrocarbon, or an acetylenic compound.
 71. The method ofclaim 54, wherein the water insoluble defoamer is at least one of nonylphenol, polypropylene oxide, triisobutyl phosphate, kerosene, liquidparaffin, animal oil, vegetable oil, sesame oil, castor oil, alkyleneoxide, natural wax, linear or branched fatty alcohols and theiralkoxylated derivatives, octyl alcohol, hexadecyl alcohol, acetylenicalcohol, acetylinic alcohol alkoxylates, glycols, polyoxyalkyleneglycol, polyoxyalkylene amide, acrylate polyamine, tributyl phosphate,silicone oil, silicone paste, silicone emulsion, organic modifiedpolysiloxane, fluorosilicone oil; and or polyoxyethylenepolyoxypropylene adducts.
 72. The method of claim 54, wherein the cementis selected from the group consisting of portland cement, masonrycement, alumina cement, refractory cement, magnesia cement, calciumsulfoaluminate cement, oil well cement, and mixtures thereof.
 73. Themethod of claim 54 further comprising mixing a cement admixture oradditive into the cementitious composition, wherein the cement admixtureor additive is at least one of set accelerators, set retarders, airdetraining agents, foaming agents, dampproofing admixtures pumping aids,fungicidal admixtures, insecticidal admixtures, germicidal admixtures,alkali activity reducers, bonding admixtures, corrosion inhibitors,pozzolans, clay, pigments, or aggregates.
 74. The method of claim 73wherein the aggregate is at least one of silica, quartz, crushed roundmarble, glass sphere, granite, limestone, calcite, feldspar, alluvialsands, or sand.
 75. The method of claim 73, wherein the pozzolan is atleast one of natural pozzolan, fly ash, silica fume, calcined clay, orblast furnace slag.
 76. The method of claim 54, wherein prior toaddition to cementitious material the amine solubilizing agent ispresent in an amount sufficient to form a stable micellar solution. 77.The method of claim 54, wherein the water insoluble defoamer, the aminesolubilizing agent capable of solubilizing the water insoluble defoamer,and optionally the dispersant for cementitious compositions are added asone solution to cementitious material.